The technology of solid-state lighting has developed for decades in various industries.Phosphor,as an element part,determines the application domain of lighting products.For instance,blue and redemitting phosphors are...The technology of solid-state lighting has developed for decades in various industries.Phosphor,as an element part,determines the application domain of lighting products.For instance,blue and redemitting phosphors are required in the process of plant supplementing light,arrow-band emitting phosphors are applied to backlight displays,etc.In this work,a Bi^(3+)-activated blue phosphor was obtained in a symmetrical and co mpact crystal structure of Gd3Sb07(GSO).Then,the co-doping strategy of alkali metal ions(Li^(+),Na^(+),and K^(+))was used to optimize the performance.The result shows that the photoluminescence intensity is increased by 2.1 times and 1.3 times respectively by introducing Li~+and K^(+)ions.Not only that,it also achieves narrow-band emitting with the full width of half-maximum(FWHM)reaching 42 nm through Na^(+)doping,and its excitation peak position also shifts from 322 to 375 nm,which can be well excited by near-ultraviolet(NUV)light emitting diode(LED)chips(365 nm).Meanwhile,the electroluminescence spectrum of GSO:0.6 mol%Bi^(3+),3 wt%Na^(+)matches up to 93.39%of the blue part of the absorption spectrum of chlorophyll a.In summary,the Bi^(3+)-activated blue phosphor reported in this work can synchronously meet the requirements of plant light replenishment and field emission displays.展开更多
The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory ca...The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.展开更多
A series of CaFCl：Tb3＋ and CaFCI：Tb3＋,A＋ （A=Li, Na and K） nanophosphors were synthesized by the one-step sol-gel method, which were reported for the first time. The sample consisted of monodisperse particles, t...A series of CaFCl：Tb3＋ and CaFCI：Tb3＋,A＋ （A=Li, Na and K） nanophosphors were synthesized by the one-step sol-gel method, which were reported for the first time. The sample consisted of monodisperse particles, the average size of which was 37 nm. The emissions of Tb3＋ ions and oxygen defects OF＇ were demonstrated in the CaFCl：Tb3＋ samples. The former was made up of several peaks at 488, 545, 587 and 623 nm, ascribed to 5D4→7FJ （j=6-3） transitions of Tb3＋ ions. The latter was shown as a broad band peaked at about 450 nm. Alkali metal ions A＋ （A=Li, Na and K） were introduced as the charge compensators to improve the luminescence of samples. The influence of charge compensators on the emissions of Tb3＋ ions and oxygen defects OF＇ was investigated by the measurement of fluorescence spectra and luminescence decay curves. The results indicated that all the charge compensators weakened the defects emission. Furthermore, Li＋ ion was the best charge compensator, because it not only reduced the defects emission but also increased the emission intensity of Tb3＋ significantly. Our results suggested that this nanophosphor sensitized by the charge compensator might broaden potential applications of rare-earth doped CaFCl.展开更多
A series of red emitting ZnTiO3 phosphors co-doped with Eu3＋） and alkali metal ions（Li＋, Na＋ and K＋） was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffra...A series of red emitting ZnTiO3 phosphors co-doped with Eu3＋） and alkali metal ions（Li＋, Na＋ and K＋） was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffraction（XRD） and transmission electron microscopy（TEM） after annealing at 700 ℃. The results show that the crystal structure belongs to the hexagonal phase of ZnTiO3 with space group R-3：R. The influence of site occupancy of different alkali metal ions on the emission of ZnTiO3：Eu3＋） phosphors was investigated in detail. The emission intensity was significantly enhanced by introducing alkali metal ions. In contrast to Eu3＋） singly doped ZnTiO3, the red emission intensities of ZnTiO3：Eu3＋） with 4 mol% alkali metal ions（Li＋, Na＋, K＋） were enhanced by about 2.1, 1.7 and 1.4 times, respectively. In addition, the Commission Internationale Ed I＇eclairage（CIE） chromaticity coordinates of ZnTiO3：Eu3＋）, Li＋（0.672, 0.328） are quite similar to the National Television Standard Committee（NTSC） standard values for the red（0.670, 0.380）.展开更多
Sulfur dioxide(SO_(2))emissions from diesel exhaust pose a serious threat to the environment and human health.Thus,desulfurization technology and the performance of desulfurization materials must be improved.In this s...Sulfur dioxide(SO_(2))emissions from diesel exhaust pose a serious threat to the environment and human health.Thus,desulfurization technology and the performance of desulfurization materials must be improved.In this study,MnO_(2) was modified with various alkali metal ions using the impregnation method to enhance its SO_(2) capture performance.The composites were characterized intensively by scanning electron microscopy,energydispersive X-ray spectroscopy,X-ray diffraction spectroscopy,and Brunauer-Emmett-Teller theory.The SO_(2) capture performance of these composites were measured via thermogravimetry,and the effect of doping with alkali metal ions on the SO_(2) capture performance of MnO_(2) was investigated.Results showed that the SO_(2) capture performance of MnO_(2) could be enhanced by doping with alkali metal ions,and the MnO_(2) composite doped with LiOH(2.0 mol/L)had the best SO_(2) capture capacity(124 mgSO_(2)/gMaterial),which was 18%higher than that of pure MnO_(2).Moreover,the type and concentration of alkali metal ions had varying effects on the SO_(2) capture performance of MnO_(2).In our experiment,the SO_(2) capture performance of the MnO_(2) doped with NaOH,LiCl,Na2CO3,K2CO3,and Li2CO3 composites were worse than that of pure MnO_(2).Therefore,the influences of the type and concentration of alkali metal ions to be doped into desulfurization materials must be considered comprehensively.展开更多
EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluoresc...EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.展开更多
We study the influence of alkali oxides on the near-infrared（NIR）-emitting thermal stability of Bi-doped R2O–Si O2–B2O3–Al2O3（R = Li, Na, K） glasses below Tg. Results show that undergoing heat treatment, remark...We study the influence of alkali oxides on the near-infrared（NIR）-emitting thermal stability of Bi-doped R2O–Si O2–B2O3–Al2O3（R = Li, Na, K） glasses below Tg. Results show that undergoing heat treatment, remarkable luminescence quenching occurs for the glasses containing Na2 O and K2 O due to the formation of Bi metallic colloids, whereas the glass with Li2 O shows much better thermal stability. These changes can be understood by the tendency of modifier cations with lower mobility and higher tightness network to restrain the transport of Bi-related NIR-emitting centers. The results provide a scientific reference for composition design of Bi-doped optical fiber.展开更多
This paper reported the thermal stability and spectroscopic properties of Ga2O3-GeO2-Na2O-K2O （GGNK） glasses doped with Er3＋. The GGNK glasses were characterized by differential scanning calorimetry （DSC）, Raman ...This paper reported the thermal stability and spectroscopic properties of Ga2O3-GeO2-Na2O-K2O （GGNK） glasses doped with Er3＋. The GGNK glasses were characterized by differential scanning calorimetry （DSC）, Raman spectra, absorption and infra- red-visible fluorescence spectra. Measured DSC result showed that these glasses possessed an excellent stability （AT=188.6 ℃）. The relationship between glass composition and Judd-Ofelt intensity parameters and other optical properties of Er3＋, such as the absorption and stimulated emission cross-sections, were clarified. Meanwhile an intense broadband 1.53μm emission with a full width at half- maximum of 51 nm and peak emission cross-section of 9.32×10^-21 cm2 of Er3＋-doped GGNK glass was obtained upon 980 nm di- ode-laser excitation. Effects of K2O replacing Na2O on the thermal stability and spectroscopic properties were investigated. It was found that the incorporation of K2O into Er3＋-doped Ga2O3-GeO2-Na2O glass could effectively improve the 1.53 μm emission luminescence. The results showed that GGNK glass might be more attractive host material for their application in C-band optical fiber amplifiers.展开更多
Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.De...Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.展开更多
Based on the density functional theory calculations,we have investigated the feasibility of two-dimensionalβ-GeS monolayer as high-performance anodes for alkali metal ion batteries.The results show that the electrica...Based on the density functional theory calculations,we have investigated the feasibility of two-dimensionalβ-GeS monolayer as high-performance anodes for alkali metal ion batteries.The results show that the electrical conductivity of β-GeS monolayer can be enhanced after adsorbing the alkali metal atoms owing to the semiconductor-to-metal transition.The low diffusion barriers of alkali metal atoms on the β-GeS surface indicate a rapid charge/discharge rate without metal clustering.Moreover,the low average open-circuit voltage(0.211 V)and a high theoretical capacity(1024 mAh·g^(-1))for Na suggest that theβ-GeS monolayer is a promising anode material for Na-ion batteries with high performance.展开更多
Hollow nanostructures are extremely attractive in energy storage and show broad application prospects.But the preparation method is accompanied by a complicated process.In this article,the CoZn-based hol-low nanoboxes...Hollow nanostructures are extremely attractive in energy storage and show broad application prospects.But the preparation method is accompanied by a complicated process.In this article,the CoZn-based hol-low nanoboxes with electrochemical synergy are prepared in a simple way.This structure can effectively shorten the transmission distance of ions and electrons,and alleviate the volume expansion during the cycle.In particular,bimetallic oxides are rich in oxygen vacancies,providing more active sites for electro-chemical reactions.In addition,the stepwise oxidation-reduction reaction can also improve the volume change of the electrode material.According to the kinetic analysis and density functional theory(DFT)calculation,it is confirmed that the synergistic effect of the bimetallic oxide can accelerate the reaction kinetics.Based on these characteristics,the electrode exhibits stable cycle performance and long cycle life in alkali metal ion batteries,and can provide reversible capacities of 302.1(LIBs,2000 cycles),172.5(SIBs,10000 cycles)and 109.6(PIBs,5000 cycles)mA h g^(-1)at a current density of 1.0 A g^(-1),respectively.In ad-dition,by assembling(LiCoO_(2)//CoZn-O_(2))and(Na_(3)V_(2)(PO_(4))_(3)//CoZn-O_(2))full-cells,the practical application value is demonstrated.The sharing of this work introduces a simple way to synthesize hollow nanoboxes,and shows excellent electrochemical performance,which can also be expanded in other areas.展开更多
Alloyed based anode materials with high theoretical specific capacity and low reaction potential are considered to be highly potential high-energy density anode materials for alkali metal ion batteries(AMIBs).Thus,the...Alloyed based anode materials with high theoretical specific capacity and low reaction potential are considered to be highly potential high-energy density anode materials for alkali metal ion batteries(AMIBs).Thus,the design of alloyed based materials with high electrochemical performance has attracted great attention.Among the numerous characterization methods for guiding electrode materials design,in situ transmission electron microscopy(TEM)gradually plays an irreplaceable role due to its high temporal and spatial resolution in directly observing the change of morphology,crystal structure and element evolutions.Herein,we reviewed the two current research hotspots and mainly focused on the structure design of alloyed based electrode material under the guidance of in situ TEM.Specifically,various nanostructure designs of alloyed based electrode materials with guidance of in situ TEM were employed to solve the key scientific issues of the violent volume change during alloying/dealloying processes for enhanced electrochemical performances.Mainly through introducing buffer space in the electrode material to reduce volume change to improve structural stability,including porous structure(0 D),nanotube structure(1 D),simple hollow structure,yolk-shell structure and some hybrid hollow structures(3 D).Furthermore,the direct guidance of in situ TEM is expected for creating new opportunities to nextgeneration electrode material design for AMIBs.展开更多
Carbon nitride,a typical low-dimensional conjugated polymer photocatalyst,features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and...Carbon nitride,a typical low-dimensional conjugated polymer photocatalyst,features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes.The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity.In this paper,by introducing a variety of polar metal cations to carbon nitride,it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization,which effectively promotes the dissociation of excitons into electrons and holes.The sodium ion shows the best modification effect,which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50%.Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride.This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.展开更多
Thispaper has investigated the coordination and supramolecular assemblies of alkali metal ions,cucurbit[5]uril(Q[5]),and[CdCl_(4)]^(2-)to confirm whether[CdCl_(4)]^(2-)can produce the“honeycomb effect”,induce coordi...Thispaper has investigated the coordination and supramolecular assemblies of alkali metal ions,cucurbit[5]uril(Q[5]),and[CdCl_(4)]^(2-)to confirm whether[CdCl_(4)]^(2-)can produce the“honeycomb effect”,induce coordination of alkali metal ions to Q[5],and form linear coordination polymers.In this work,the effect of alkali metal ions on the construction of Q[5]-Cd^(2+)ion system under acidic conditions was investigated.Five complexes were successfully obtained by solvent evaporation method.Among the five crystal structures obtained,it can be observed that the presence of[CdCl_(4)]^(2-)did not result in the complexation of alkali metal ions by the Q[5]molecule.Instead,a bowl-like Cd^(2+)@Q[5]complex was formed.Indeed,[CdCl_(4)]^(2-)did not produce the honeycomb effect but led to the formation of Q[5]-based honeycomb frameworks with hexagonal cellsoccupied by[CdCl_(4)]^(2-).The experimental results show that cadmium ion showed stronger ability to coordinate to Q[5]in HCl solution.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
DNA and its conformational transition can be used to design nanometer-scale structures, nano-tweezers and nanomechanical devices. Experiments and molecular simulations have been used to study the concentration effect ...DNA and its conformational transition can be used to design nanometer-scale structures, nano-tweezers and nanomechanical devices. Experiments and molecular simulations have been used to study the concentration effect on the A-DNA→B-DNA conformational transition, but a systematical investigation on counterion effect on the dynamics of this transition has not been reported up to now. In present work, restrained and unrestrained molecular dynamics （MD） simulations have been performed to characterize the stability of DNA conformations and the dynamics of A-DNA→B-DNA transitions in aqueous solutions with different alkali metal counterions. The DNA duplex d（CGCGAATTCGCG）2, coion Cl- and counterions Li＋, Na＋, K＋, Rb＋ and Cs~ as well as water molecule were considered using the PARM99 force field in the AMBER8 package. It was found that B-form DNA is more stable than A-form DNA in aqueous electrolyte solutions with different alkali metal counterions. In- creasing KCI concentration in solution hinders the A-DNA^B-DNA transition and the transition times for different alkali metal counterions conform to neither the simple sequence related to naked ion size nor to hydrated diameter, but an apparently abnormal sequence of K＋ 〈 Rb＋ 〈 Cs＋ 〈 Na＋ 〈 Li＋. This abnormal sequence can be well understood in terms of an electrostatic model based on the effective cation diameters and the modified mean-spherical approximation （MMSA）. The present results provide valuable information for the design of DNA-based nanomaterials and nanodevices.展开更多
As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they sti...As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they still face challenges,such as low room-temperature ionic conductivity,narrow electrochemical windows,and poor mechanical strength.To realize the practical application of all-solid-state alkali metal ion batteries,there has been a lot of research on modifying the chemical composition or structure of polymerbased SSEs.In this review,the transport mechanism of alkali metal ions in polymer SSEs is briefly introduced.We systematically summarize the recent strategies to improve polymer-based SSEs,which have been validated in lithium-ion batteries and sodium-ion batteries,including lamellar electrolyte structure,dual salts hybridization,oriented filler alignment,and so on.Then,taking the unique properties of potassium metal and potassium ions into consideration,the feasibility of potassium-ion batteries for practical use enabled by these novel modification methods is discussed.展开更多
Sb-based materials with high specific capacity have targeted as an alternative anode material for alkali metal ion batteries.Herein,Sb nanoparticles embedded in hollow porous N-doped carbon nanotubes(Sb@N-C nanotubes)...Sb-based materials with high specific capacity have targeted as an alternative anode material for alkali metal ion batteries.Herein,Sb nanoparticles embedded in hollow porous N-doped carbon nanotubes(Sb@N-C nanotubes)are used as freestanding anode for Li-ion batteries(LIBs)and K-ion batteries(PIBs).The Sb@N-C nanotubes demonstrate exceptional reversible capacity of643 mAh·g^(-1)at 0.1 A·g^(-1)with long cycle stability,as well as outstanding rate performance(219.6 mAh·g^(-1)at10 A·g^(-1))in LIBs.As the anode material of PIBs,they reveal impressive capacity of 325.4 mAh·g^(-1)at 0.1 A·g^(-1).The superior electrochemical properties mainly originate from the novel structure.To be specific,the obtained 3D connected network allows for quick ion and electron migration,and prevents the aggregation of Sb nanoparticles.The hollow porous nanotubes can not only accommodate the volume expansion of Sb nanoparticles during cycling,but also facilitate the infiltration of the electrolyte and reduce the ion diffusion length.This work provides a new insight for designing advanced Sb-based anodes for alkali metal ion batteries.展开更多
Hard carbon,a prominent member of carbonaceous materials,shows immense potential as a high-performance anode for energy storage in batteries,attracting significant attention.Its structural diversity offers superior pe...Hard carbon,a prominent member of carbonaceous materials,shows immense potential as a high-performance anode for energy storage in batteries,attracting significant attention.Its structural diversity offers superior performance and high tunability,making it ideal for use as an anode in lithium-ion batteries,sodium-ion batteries,and potassium-ion batteries.To develop higher-performance hard carbon anode materials,extensive research has been conducted to understand the storage mechanisms of alkali metal ions in hard carbon.Building on this foundation,this paper provides an in-depth review of the relationship between the structure of hard carbon and its electrochemical properties with alkali metal ions.It emphasizes the structural design and characterization of hard carbon,the storage mechanisms of alkali metal ions,and key strategies for structural modulation.Additionally,it offers a forward-looking perspective on the future potential of hard carbon.This review aims to provide a comprehensive overview of the current state of hard carbon anodes in battery research and highlights the promising future of this rapidly evolving field in advancing the development of next-generation alkali metal-ion batteries.展开更多
Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries(AMIBs).However,the general behavior of space char...Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries(AMIBs).However,the general behavior of space charge storage in AMIBs has been less investigated experimentally,mostly due to the complicated electrochemical behavior and lack of proper characterization techniques.Here,we use operando magnetometry to verify that in FeSe_(2)AMIBs,abundant Li^(+)/Na^(+)/K^(+)(M^(+))can be stored at M_(2)Se phase while electrons accumulate at Fe nanoparticles,forming interfacial space charge layers.Magnetic and dynamics tests further demonstrate that with increasing ionic radius from Li^(+),Na^(+)to K^(+),the reaction kinetics can be hindered,resulting in limited Fe formation and reduced space charge storage capacity.This work lays solid foundation for studying the complex interfacial effect in electrochemical processes and designing advanced energy storage devices with substantial capacity and considerable power density.展开更多
基金Project supported by the Key R&D Projects in Hunan Province(2021SK2047,2022NK2044)Science and Technology Innovation Program of Hunan Province(2022WZ1022)Superior Youth Project of the Science Research Project of Hunan Provincial Department of Education(22B0211)。
文摘The technology of solid-state lighting has developed for decades in various industries.Phosphor,as an element part,determines the application domain of lighting products.For instance,blue and redemitting phosphors are required in the process of plant supplementing light,arrow-band emitting phosphors are applied to backlight displays,etc.In this work,a Bi^(3+)-activated blue phosphor was obtained in a symmetrical and co mpact crystal structure of Gd3Sb07(GSO).Then,the co-doping strategy of alkali metal ions(Li^(+),Na^(+),and K^(+))was used to optimize the performance.The result shows that the photoluminescence intensity is increased by 2.1 times and 1.3 times respectively by introducing Li~+and K^(+)ions.Not only that,it also achieves narrow-band emitting with the full width of half-maximum(FWHM)reaching 42 nm through Na^(+)doping,and its excitation peak position also shifts from 322 to 375 nm,which can be well excited by near-ultraviolet(NUV)light emitting diode(LED)chips(365 nm).Meanwhile,the electroluminescence spectrum of GSO:0.6 mol%Bi^(3+),3 wt%Na^(+)matches up to 93.39%of the blue part of the absorption spectrum of chlorophyll a.In summary,the Bi^(3+)-activated blue phosphor reported in this work can synchronously meet the requirements of plant light replenishment and field emission displays.
基金supported by the National Key Research Development Program of China(2017YFB0601900)National Nature Science Foundation of China(51806220,51922040),China Postdoctoral Science Foundation(2019TQ0091)+1 种基金Grants from Fok Ying Tung Education Foundation(161051)Fundamental Research Funds for the Central Universities(2020MS020,2020DF01).
文摘The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.
基金Project supported by the National Natural Science Foundation of China(11204039,51202033)the Science Foundation of the Educational Department of Fujian Province of China(JA13084)the Natural Science Foundation of Fujian Province of China(2015J01243)
文摘A series of CaFCl：Tb3＋ and CaFCI：Tb3＋,A＋ （A=Li, Na and K） nanophosphors were synthesized by the one-step sol-gel method, which were reported for the first time. The sample consisted of monodisperse particles, the average size of which was 37 nm. The emissions of Tb3＋ ions and oxygen defects OF＇ were demonstrated in the CaFCl：Tb3＋ samples. The former was made up of several peaks at 488, 545, 587 and 623 nm, ascribed to 5D4→7FJ （j=6-3） transitions of Tb3＋ ions. The latter was shown as a broad band peaked at about 450 nm. Alkali metal ions A＋ （A=Li, Na and K） were introduced as the charge compensators to improve the luminescence of samples. The influence of charge compensators on the emissions of Tb3＋ ions and oxygen defects OF＇ was investigated by the measurement of fluorescence spectra and luminescence decay curves. The results indicated that all the charge compensators weakened the defects emission. Furthermore, Li＋ ion was the best charge compensator, because it not only reduced the defects emission but also increased the emission intensity of Tb3＋ significantly. Our results suggested that this nanophosphor sensitized by the charge compensator might broaden potential applications of rare-earth doped CaFCl.
基金Supported by Department of Social Development Project of Jiangsu Province(BE2015659)Science and Technology Project of Anhui Province(1604a0802122)Collaborative Innovation Center Project in Jiangsu Province(GX2015302)
文摘A series of red emitting ZnTiO3 phosphors co-doped with Eu3＋） and alkali metal ions（Li＋, Na＋ and K＋） was prepared by sol-gel method. The crystal structure of the phosphors was investigated by using X-ray diffraction（XRD） and transmission electron microscopy（TEM） after annealing at 700 ℃. The results show that the crystal structure belongs to the hexagonal phase of ZnTiO3 with space group R-3：R. The influence of site occupancy of different alkali metal ions on the emission of ZnTiO3：Eu3＋） phosphors was investigated in detail. The emission intensity was significantly enhanced by introducing alkali metal ions. In contrast to Eu3＋） singly doped ZnTiO3, the red emission intensities of ZnTiO3：Eu3＋） with 4 mol% alkali metal ions（Li＋, Na＋, K＋） were enhanced by about 2.1, 1.7 and 1.4 times, respectively. In addition, the Commission Internationale Ed I＇eclairage（CIE） chromaticity coordinates of ZnTiO3：Eu3＋）, Li＋（0.672, 0.328） are quite similar to the National Television Standard Committee（NTSC） standard values for the red（0.670, 0.380）.
基金This work was financially supported by the Key Program of Frontier Science of Chinese Academy of Sciences(QYZDY-SSW-JSC038)the Natural Science Foundation of Guangdong Province(2017A030310185)the Science and Technology Planning Project of Guangzhou,China(201704030040).
文摘Sulfur dioxide(SO_(2))emissions from diesel exhaust pose a serious threat to the environment and human health.Thus,desulfurization technology and the performance of desulfurization materials must be improved.In this study,MnO_(2) was modified with various alkali metal ions using the impregnation method to enhance its SO_(2) capture performance.The composites were characterized intensively by scanning electron microscopy,energydispersive X-ray spectroscopy,X-ray diffraction spectroscopy,and Brunauer-Emmett-Teller theory.The SO_(2) capture performance of these composites were measured via thermogravimetry,and the effect of doping with alkali metal ions on the SO_(2) capture performance of MnO_(2) was investigated.Results showed that the SO_(2) capture performance of MnO_(2) could be enhanced by doping with alkali metal ions,and the MnO_(2) composite doped with LiOH(2.0 mol/L)had the best SO_(2) capture capacity(124 mgSO_(2)/gMaterial),which was 18%higher than that of pure MnO_(2).Moreover,the type and concentration of alkali metal ions had varying effects on the SO_(2) capture performance of MnO_(2).In our experiment,the SO_(2) capture performance of the MnO_(2) doped with NaOH,LiCl,Na2CO3,K2CO3,and Li2CO3 composites were worse than that of pure MnO_(2).Therefore,the influences of the type and concentration of alkali metal ions to be doped into desulfurization materials must be considered comprehensively.
文摘EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.
基金supported by the National Natural Science Foundation of China under Grant Nos.61265007,61265004,and 51272097
文摘We study the influence of alkali oxides on the near-infrared（NIR）-emitting thermal stability of Bi-doped R2O–Si O2–B2O3–Al2O3（R = Li, Na, K） glasses below Tg. Results show that undergoing heat treatment, remarkable luminescence quenching occurs for the glasses containing Na2 O and K2 O due to the formation of Bi metallic colloids, whereas the glass with Li2 O shows much better thermal stability. These changes can be understood by the tendency of modifier cations with lower mobility and higher tightness network to restrain the transport of Bi-related NIR-emitting centers. The results provide a scientific reference for composition design of Bi-doped optical fiber.
基金Project supported by the National Natural Science Foundation of China(51002070)Funding Scheme for Young Teachers ofHigher School in Henan Province(2012GGJS-192)
文摘This paper reported the thermal stability and spectroscopic properties of Ga2O3-GeO2-Na2O-K2O （GGNK） glasses doped with Er3＋. The GGNK glasses were characterized by differential scanning calorimetry （DSC）, Raman spectra, absorption and infra- red-visible fluorescence spectra. Measured DSC result showed that these glasses possessed an excellent stability （AT=188.6 ℃）. The relationship between glass composition and Judd-Ofelt intensity parameters and other optical properties of Er3＋, such as the absorption and stimulated emission cross-sections, were clarified. Meanwhile an intense broadband 1.53μm emission with a full width at half- maximum of 51 nm and peak emission cross-section of 9.32×10^-21 cm2 of Er3＋-doped GGNK glass was obtained upon 980 nm di- ode-laser excitation. Effects of K2O replacing Na2O on the thermal stability and spectroscopic properties were investigated. It was found that the incorporation of K2O into Er3＋-doped Ga2O3-GeO2-Na2O glass could effectively improve the 1.53 μm emission luminescence. The results showed that GGNK glass might be more attractive host material for their application in C-band optical fiber amplifiers.
基金the National Key R&D Research Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant Nos.51872277,21606003,51902062,51972067,51802044,51925207 and U1910210)+2 种基金the Fundamental Research Funds for the Central Universities(WK2060140026)the DNL cooperation Fund,CAS(DNL180310)the Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)。
文摘Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.
基金Project supported by the the National Natural Science Foundation of China(Grant Nos.52062035 and 51861023)the Major Discipline Academic and Technical Leaders Training Program of Jiangxi Province,China(Grant No.20213BCJ22056).
文摘Based on the density functional theory calculations,we have investigated the feasibility of two-dimensionalβ-GeS monolayer as high-performance anodes for alkali metal ion batteries.The results show that the electrical conductivity of β-GeS monolayer can be enhanced after adsorbing the alkali metal atoms owing to the semiconductor-to-metal transition.The low diffusion barriers of alkali metal atoms on the β-GeS surface indicate a rapid charge/discharge rate without metal clustering.Moreover,the low average open-circuit voltage(0.211 V)and a high theoretical capacity(1024 mAh·g^(-1))for Na suggest that theβ-GeS monolayer is a promising anode material for Na-ion batteries with high performance.
基金supported by the National Natural Science Foundation of China(No:52072307)。
文摘Hollow nanostructures are extremely attractive in energy storage and show broad application prospects.But the preparation method is accompanied by a complicated process.In this article,the CoZn-based hol-low nanoboxes with electrochemical synergy are prepared in a simple way.This structure can effectively shorten the transmission distance of ions and electrons,and alleviate the volume expansion during the cycle.In particular,bimetallic oxides are rich in oxygen vacancies,providing more active sites for electro-chemical reactions.In addition,the stepwise oxidation-reduction reaction can also improve the volume change of the electrode material.According to the kinetic analysis and density functional theory(DFT)calculation,it is confirmed that the synergistic effect of the bimetallic oxide can accelerate the reaction kinetics.Based on these characteristics,the electrode exhibits stable cycle performance and long cycle life in alkali metal ion batteries,and can provide reversible capacities of 302.1(LIBs,2000 cycles),172.5(SIBs,10000 cycles)and 109.6(PIBs,5000 cycles)mA h g^(-1)at a current density of 1.0 A g^(-1),respectively.In ad-dition,by assembling(LiCoO_(2)//CoZn-O_(2))and(Na_(3)V_(2)(PO_(4))_(3)//CoZn-O_(2))full-cells,the practical application value is demonstrated.The sharing of this work introduces a simple way to synthesize hollow nanoboxes,and shows excellent electrochemical performance,which can also be expanded in other areas.
基金supported by the National Natural Science Foundation of China(No.51621001)the National Key Research and Development Program of China(No.2016YFA0202604)Key Laboratory of Resource Chemistry,Ministry of Education Joint International Research Laboratory of Resource Chemistry and the open fund from Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion(No.2018TP1037-202005)。
文摘Alloyed based anode materials with high theoretical specific capacity and low reaction potential are considered to be highly potential high-energy density anode materials for alkali metal ion batteries(AMIBs).Thus,the design of alloyed based materials with high electrochemical performance has attracted great attention.Among the numerous characterization methods for guiding electrode materials design,in situ transmission electron microscopy(TEM)gradually plays an irreplaceable role due to its high temporal and spatial resolution in directly observing the change of morphology,crystal structure and element evolutions.Herein,we reviewed the two current research hotspots and mainly focused on the structure design of alloyed based electrode material under the guidance of in situ TEM.Specifically,various nanostructure designs of alloyed based electrode materials with guidance of in situ TEM were employed to solve the key scientific issues of the violent volume change during alloying/dealloying processes for enhanced electrochemical performances.Mainly through introducing buffer space in the electrode material to reduce volume change to improve structural stability,including porous structure(0 D),nanotube structure(1 D),simple hollow structure,yolk-shell structure and some hybrid hollow structures(3 D).Furthermore,the direct guidance of in situ TEM is expected for creating new opportunities to nextgeneration electrode material design for AMIBs.
基金supported by the National Natural Science Foundation of China(Nos.22002107,21905202,22179093)。
文摘Carbon nitride,a typical low-dimensional conjugated polymer photocatalyst,features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes.The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity.In this paper,by introducing a variety of polar metal cations to carbon nitride,it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization,which effectively promotes the dissociation of excitons into electrons and holes.The sodium ion shows the best modification effect,which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50%.Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride.This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.
文摘Thispaper has investigated the coordination and supramolecular assemblies of alkali metal ions,cucurbit[5]uril(Q[5]),and[CdCl_(4)]^(2-)to confirm whether[CdCl_(4)]^(2-)can produce the“honeycomb effect”,induce coordination of alkali metal ions to Q[5],and form linear coordination polymers.In this work,the effect of alkali metal ions on the construction of Q[5]-Cd^(2+)ion system under acidic conditions was investigated.Five complexes were successfully obtained by solvent evaporation method.Among the five crystal structures obtained,it can be observed that the presence of[CdCl_(4)]^(2-)did not result in the complexation of alkali metal ions by the Q[5]molecule.Instead,a bowl-like Cd^(2+)@Q[5]complex was formed.Indeed,[CdCl_(4)]^(2-)did not produce the honeycomb effect but led to the formation of Q[5]-based honeycomb frameworks with hexagonal cellsoccupied by[CdCl_(4)]^(2-).The experimental results show that cadmium ion showed stronger ability to coordinate to Q[5]in HCl solution.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金supported by the National Natural Science Foundation of China(21176132 and 20876083)Specialized Research Fund for the Doctoral Program of Higher Education(20100002110024)
文摘DNA and its conformational transition can be used to design nanometer-scale structures, nano-tweezers and nanomechanical devices. Experiments and molecular simulations have been used to study the concentration effect on the A-DNA→B-DNA conformational transition, but a systematical investigation on counterion effect on the dynamics of this transition has not been reported up to now. In present work, restrained and unrestrained molecular dynamics （MD） simulations have been performed to characterize the stability of DNA conformations and the dynamics of A-DNA→B-DNA transitions in aqueous solutions with different alkali metal counterions. The DNA duplex d（CGCGAATTCGCG）2, coion Cl- and counterions Li＋, Na＋, K＋, Rb＋ and Cs~ as well as water molecule were considered using the PARM99 force field in the AMBER8 package. It was found that B-form DNA is more stable than A-form DNA in aqueous electrolyte solutions with different alkali metal counterions. In- creasing KCI concentration in solution hinders the A-DNA^B-DNA transition and the transition times for different alkali metal counterions conform to neither the simple sequence related to naked ion size nor to hydrated diameter, but an apparently abnormal sequence of K＋ 〈 Rb＋ 〈 Cs＋ 〈 Na＋ 〈 Li＋. This abnormal sequence can be well understood in terms of an electrostatic model based on the effective cation diameters and the modified mean-spherical approximation （MMSA）. The present results provide valuable information for the design of DNA-based nanomaterials and nanodevices.
基金Fundamental Research Funds for the Central Universities,Grant/Award Number:FRF-IDRY-21-013National Natural Science Foundation of China,Grant/Award Numbers:52371131,52474318+1 种基金Beijing Nova Program,Grant/Award Number:Z211100002121082State Key Laboratory of Explosion Science and Technology,Grant/Award Number:QNKT23-05。
文摘As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they still face challenges,such as low room-temperature ionic conductivity,narrow electrochemical windows,and poor mechanical strength.To realize the practical application of all-solid-state alkali metal ion batteries,there has been a lot of research on modifying the chemical composition or structure of polymerbased SSEs.In this review,the transport mechanism of alkali metal ions in polymer SSEs is briefly introduced.We systematically summarize the recent strategies to improve polymer-based SSEs,which have been validated in lithium-ion batteries and sodium-ion batteries,including lamellar electrolyte structure,dual salts hybridization,oriented filler alignment,and so on.Then,taking the unique properties of potassium metal and potassium ions into consideration,the feasibility of potassium-ion batteries for practical use enabled by these novel modification methods is discussed.
基金financially supported by the National Key Research and Development Program of China(No.2019YFB2205005)the Natural Science Foundation of Fujian Province(No.2020 JO1050)。
文摘Sb-based materials with high specific capacity have targeted as an alternative anode material for alkali metal ion batteries.Herein,Sb nanoparticles embedded in hollow porous N-doped carbon nanotubes(Sb@N-C nanotubes)are used as freestanding anode for Li-ion batteries(LIBs)and K-ion batteries(PIBs).The Sb@N-C nanotubes demonstrate exceptional reversible capacity of643 mAh·g^(-1)at 0.1 A·g^(-1)with long cycle stability,as well as outstanding rate performance(219.6 mAh·g^(-1)at10 A·g^(-1))in LIBs.As the anode material of PIBs,they reveal impressive capacity of 325.4 mAh·g^(-1)at 0.1 A·g^(-1).The superior electrochemical properties mainly originate from the novel structure.To be specific,the obtained 3D connected network allows for quick ion and electron migration,and prevents the aggregation of Sb nanoparticles.The hollow porous nanotubes can not only accommodate the volume expansion of Sb nanoparticles during cycling,but also facilitate the infiltration of the electrolyte and reduce the ion diffusion length.This work provides a new insight for designing advanced Sb-based anodes for alkali metal ion batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.92372101,52122211,52072323 and 21875155)the Fundamental Research Funds for the Central Universities(No.20720220010)+2 种基金the National Key Research and Development Program of China(No.2021YFA1201502)the Frontier Exploration Projects of Longmen Laboratory(grant No.LMQYTSKT008)the Shenzhen Technical Plan Project(No.JCYJ20220818101003008).
文摘Hard carbon,a prominent member of carbonaceous materials,shows immense potential as a high-performance anode for energy storage in batteries,attracting significant attention.Its structural diversity offers superior performance and high tunability,making it ideal for use as an anode in lithium-ion batteries,sodium-ion batteries,and potassium-ion batteries.To develop higher-performance hard carbon anode materials,extensive research has been conducted to understand the storage mechanisms of alkali metal ions in hard carbon.Building on this foundation,this paper provides an in-depth review of the relationship between the structure of hard carbon and its electrochemical properties with alkali metal ions.It emphasizes the structural design and characterization of hard carbon,the storage mechanisms of alkali metal ions,and key strategies for structural modulation.Additionally,it offers a forward-looking perspective on the future potential of hard carbon.This review aims to provide a comprehensive overview of the current state of hard carbon anodes in battery research and highlights the promising future of this rapidly evolving field in advancing the development of next-generation alkali metal-ion batteries.
基金supported by the National Natural Science Foundation of China(22179066,51804173,and 11674186)the National Science Foundation of Shandong Province(ZR2020MA073)+2 种基金the Science and Technology Board of Qingdao(16-5-1-2jch)Natural Sciences and Engineering Research Council of Canada(NSERC)Discovery grant RGPIN-04178the Canada First Research Excellence Fund。
文摘Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries(AMIBs).However,the general behavior of space charge storage in AMIBs has been less investigated experimentally,mostly due to the complicated electrochemical behavior and lack of proper characterization techniques.Here,we use operando magnetometry to verify that in FeSe_(2)AMIBs,abundant Li^(+)/Na^(+)/K^(+)(M^(+))can be stored at M_(2)Se phase while electrons accumulate at Fe nanoparticles,forming interfacial space charge layers.Magnetic and dynamics tests further demonstrate that with increasing ionic radius from Li^(+),Na^(+)to K^(+),the reaction kinetics can be hindered,resulting in limited Fe formation and reduced space charge storage capacity.This work lays solid foundation for studying the complex interfacial effect in electrochemical processes and designing advanced energy storage devices with substantial capacity and considerable power density.
