Lithium(Li)metal anodes have attracted extensive attention due to their ultrahigh theoretical capacity and low potential.However,the uneven deposition of Li near the unstable electrode/electrolyte interfaces leads to ...Lithium(Li)metal anodes have attracted extensive attention due to their ultrahigh theoretical capacity and low potential.However,the uneven deposition of Li near the unstable electrode/electrolyte interfaces leads to the growth of Li dendrites and the degradation of active electrodes.Herein,we directly fluorinate alkyne-containing conjugated microporous polymers(ACMPs)microspheres with fluorine gas(F_(2))to introduce a novel fluorinated interlayer as an interfacial stabilizer in lithium metal batteries.Using density functional theory methods,it is found that as-prepared fluorinated ACMP(FACMP)has abundant partially ionic C–F bonds.The C–F bonds with electrochemical lability yield remarkable lithiophilicity during cycling.The in situ reactions between the active C–F bonds and Li ions enable transfer of lithium fluoride microcrystals to the solid electrolyte interphase(SEI)layers,guaranteeing effective ionic distribution and smooth Li deposition.Consequently,Li metal electrodes with the fluorinated interlayers demonstrate excellent cycling performances in both half-batteries and full cells with a lithium bis(trifluoromethanesulfonyl)imide electrolyte as well as a nonfluorinated lithium bis(oxalate)borate electrolyte system.This strategy is highly significant in customizable SEI layers to stabilize electrode interfaces and ensure high utilization of Li metal anodes,especially in a nonfluorinated electrolyte.展开更多
The development of all-solid-state lithium batteries(ASSLBs)depends on exploiting solid-state electrolytes(SSEs)with high ionic conductivity and electrochemical stability.Fluorination is generally considered to be an ...The development of all-solid-state lithium batteries(ASSLBs)depends on exploiting solid-state electrolytes(SSEs)with high ionic conductivity and electrochemical stability.Fluorination is generally considered to be an effective strategy to improve the ionic conductivity and electrochemical stability of inorganic SSEs.Here,we report the partial fluorination of the chlo rine sites in an antiperovskite,by which the orthorhombic Li_(2)OHCl was transformed into cubic Li_(2)OHCl_(0.9)F_(0.1),resulting in a fourfold increase in ionic conductivity at 30℃.The ab initio molecular dynamics simulations suggest that both the crystal symmetry and the anions electronegativity influence the diffusion of Li+in the antiperovskite structure.Besides,from the perspective of experiments and calculations,it is confirmed that fluorination is a feasible method to improve the electrochemical stability of antiperovskite SSEs.The LiFePO_(4)|Li cell based on Li_(2)OHCl_(0.9)F_(0.1) is also assembled and exhibits stable cycle performance,which indicates that fluorination of antiperovskite SSEs is an effective way to produce high-performance SSEs for practical application of ASSLBs.展开更多
As growing applications demand higher driving currents of oxide semiconductor thin-film transistors(TFTs),severe instabilities and even hard breakdown under high-current stress(HCS)become critical challenges.In this w...As growing applications demand higher driving currents of oxide semiconductor thin-film transistors(TFTs),severe instabilities and even hard breakdown under high-current stress(HCS)become critical challenges.In this work,the triggering voltage of HCS-induced self-heating(SH)degradation is defined in the output characteristics of amorphous indium-galliumzinc oxide(a-IGZO)TFTs,and used to quantitatively evaluate the thermal generation process of channel donor defects.The fluorinated a-IGZO(a-IGZO:F)was adopted to effectively retard the triggering of the self-heating(SH)effect,and was supposed to originate from the less population of initial deep-state defects and a slower rate of thermal defect transition in a-IGZO:F.The proposed scheme noticeably enhances the high-current applications of oxide TFTs.展开更多
Cation-disordered rocksalt oxides(DRX)have been identified as promising cathode materials for high energy density applications owing to their variable elemental composition and cationic-anionic redox activity.However,...Cation-disordered rocksalt oxides(DRX)have been identified as promising cathode materials for high energy density applications owing to their variable elemental composition and cationic-anionic redox activity.However,their practical implementation has been impeded by unwanted phenomena such as irrepressible transition metal migration/dissolution and O_(2)/CO_(2)evolution,which arise due to parasitic reactions and densification-degradation mechanisms during extended cycling.To address these issues,a micron-sized DRX cathode Li_(1.2)Ni_(1/3)Ti_(1/3)W_(2/15)O_(1.85)F_(0.15)(SLNTWOF)with F substitution and ultrathin LiF coating layer is developed by alcohols assisted sol-gel method.Within this fluorination-induced integrated structure design(FISD)strategy,in-situ F substitution modifies the activity/reversibility of the cationic-anionic redox reaction,while the ultrathin LiF coating and single-crystal structure synergistically mitigate the cathode/electrolyte parasitic reaction and densification-degradation mechanism.Attributed to the multiple modifications and size effect in the FISD strategy,the SLNTWOF sample exhibits reversible cationic-anionic redox chemistry with a meliorated reversible capacity of 290.3 mA h g^(-1)at 0.05C(1C=200 mA g^(-1)),improved cycling stability of 78.5%capacity retention after 50 cycles at 0.5 C,and modified rate capability of 102.8 mA h g^(-1)at 2 C.This work reveals that the synergistic effects between bulk structure modification,surface regulation,and engineering particle size can effectively modulate the distribution and evolution of cationic-anionic redox activities in DRX cathodes.展开更多
The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional...The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.展开更多
Previous calculations show that the two-dimensional(2 D) silicon carbide(SiC) honeycomb structure is a structurally stable monolayer. Following this, we investigate the electronic properties of the hydrogen and fluori...Previous calculations show that the two-dimensional(2 D) silicon carbide(SiC) honeycomb structure is a structurally stable monolayer. Following this, we investigate the electronic properties of the hydrogen and fluorine functionalized SiC monolayer by first-principles calculations. Our results show that the functionalized monolayer becomes metallic after semi-hydrogenation or semi-fluorination, while the semiconducting properties are obtained by the full functionalization. Compared with the bare SiC monolayer, the band gap of the fully hydrogenated system is increased, in comparison with the decrease of the gap in the fully fluorinated case. As a result, the band gap can be tuned from 0.73 to 4.14 eV by the functionalization. In addition to the metal-semiconductor transition, hydrogenation and functionalization also realize a direct-indirect semiconducting transition in the 2 D SiC monolayer. These results provide theoretical guidance for design of photoelectric devices based on the SiC monolayer.展开更多
This work treats the Al_(2)O_(3)-ER sample surface using dielectric barrier discharge fluorination(DBDF),DBD silicon deposition(DBD-Si),atmospheric-pressure plasma jet fluorination(APPJ-F)and APPJ silicon deposition(A...This work treats the Al_(2)O_(3)-ER sample surface using dielectric barrier discharge fluorination(DBDF),DBD silicon deposition(DBD-Si),atmospheric-pressure plasma jet fluorination(APPJ-F)and APPJ silicon deposition(APPJ-Si).By comparing the surface morphology,chemical components and electrical parameters,the diverse mechanisms of different plasma modification methods used to improve flashover performance are revealed.The results show that the flashover voltage of the DBDF samples is the largest(increased by 21.2%at most),while the APPJ-F method has the worst promotion effect.The flashover voltage of the APPJ-Si samples decreases sharply when treatment time exceeds 180 s,but the promotion effect outperforms the DBD-Si method during a short modified time.For the mechanism explanation,firstly,plasma fluorination improves the surface roughness and introduces shallow traps by etching the surface and grafting fluorine-containing groups,while plasma silicon deposition reduces the surface roughness and introduces a large number of shallow traps by coating Si Oxfilm.Furthermore,the reaction of the DBD method is more violent,while the homogeneity of the APPJ modification is better.These characteristics influence the effects of fluorination and silicon deposition.Finally,increasing the surface roughness and introducing shallow traps accelerates surface charge dissipation and inhibits flashover,but too many shallow traps greatly increase the dissipated rate and facilitate surface flashover instead.展开更多
Cr doped Ruddlesden-Popper compound Sr2 TiO4 has been successfully modified by fluorine to form a new compound Sr2 Ti(0.95) Cr(0.05) O3 F2. Structure analysis suggests two types of fluorine in the structure of this ne...Cr doped Ruddlesden-Popper compound Sr2 TiO4 has been successfully modified by fluorine to form a new compound Sr2 Ti(0.95) Cr(0.05) O3 F2. Structure analysis suggests two types of fluorine in the structure of this new compound, i.e. intralayer and interlayer F, which induce strong built-in electric field within this layered compound. The electric field stems from uneven distribution of F atoms on the two sides of perovskite layers therefore leads to charge disproportionation. DFT calculations suggest that this unique structural feature is highly beneficial for charge dissociations as it breaks the coplanar settlement of conduction band minimum and valence band maximum whilst maintains the 2 D charge transportation properties. This is clearly demonstrated by the superior photocatalytic activities of Sr2 Ti(0.95) Cr(0.05) O3 F2 for hydrogen production from water. Apparent quantum efficiency(AQE) as high as 1.16% at 420 ± 20 nm has been achieved which stands as the highest AQE reported on Sr2 TiO4 to date. Photoelectrochemical(PEC)analysis confirms improved charge separation conditions and prolonged charge lifetime.展开更多
The ground state rotational spectrum of 2,3,6-trifluoropyridine has been investigated in the 2.0-20.0 GHz region by pulsed jet Fourier transform microwave spectroscopy.The experimental rotational constants are A=3134....The ground state rotational spectrum of 2,3,6-trifluoropyridine has been investigated in the 2.0-20.0 GHz region by pulsed jet Fourier transform microwave spectroscopy.The experimental rotational constants are A=3134.4479(2)MHz,B=1346.79372(7)MHz,and C=941.99495(6)MHz.The transitions are so intense that rotational transitions of all mono13C and 15N isotopologues are measured in natural abundance.The semi-experimental equilibrium rotational constants of the 7 isotopologues were derived by taking account of the anharmonic vibrational corrections,which allowed a semi-experimental determination of the equilibrium structure of 2,3,6-trifluoropyridine.展开更多
A novel hybrid process for surface fluorination of polymers is being introduced. The process is based on ultra violet (UV) laser radiation, which on the one hand forms radicals out of an atmosphere of a partially fluo...A novel hybrid process for surface fluorination of polymers is being introduced. The process is based on ultra violet (UV) laser radiation, which on the one hand forms radicals out of an atmosphere of a partially fluorinated benzene, and on the other hand activates a polymer surface in the areas where the UV radiation hits the surface. The radicals can react with the polymer surface, hence altering the surface energy. With this process, a fluorine content of over 30% on the surface of bulk polystyrene can be achieved, while the smallest possible structure size was smaller than 1 mm.展开更多
Medical-grade poly(methyl methacrylate) (PMMA) is extensively employed in the fabrication of a variety of medical implants, including intraocular lenses (IOLs). However, a postoperative complication that leads to the ...Medical-grade poly(methyl methacrylate) (PMMA) is extensively employed in the fabrication of a variety of medical implants, including intraocular lenses (IOLs). However, a postoperative complication that leads to the failure of the implanted intraocular lenses has been recently identified. This process, termed calcification, occurs when calcium-containing deposits accumulate on the surface of the IOL. In this study direct gas fluorination was used to modify the surface of PMMA in an attempt to increase the service lifetime of the material in optical applications. PMMA discs exposed to a 20% fluorine/nitrogen gas mixture for 24 h were compared with untreated PMMA discs serving as control samples. Over time, both surface-fluorinated and untreated PMMA samples immersed in a simulated aqueous humour solution (SAHS) (pH 7.4, 35°C) were used to carry out in vitro studies. Attenuated total refractive Infrared spectroscopy (ATR-IR) Scanning electron microscopy (SEM), coupled with Energy dispersive X-ray analysis (EDX), showed that calcium-containing surface deposits were less abundant on surface-fluorinated PMMA compared with the control samples, indicating that the fluorinated surface was acting as a barrier to the deposits. Gravimetric analysis data showed that the decreased rate of diffusion compared with that of a control sample was due to the fluorinated surface.展开更多
Peptides have an important role in organism and its high quantity present in tumors leading to development of radiolabeled peptides for tumor-specific imaging. Once the traditional methodologies used for radiofluorina...Peptides have an important role in organism and its high quantity present in tumors leading to development of radiolabeled peptides for tumor-specific imaging. Once the traditional methodologies used for radiofluorination do not work with peptides, due to their harsh conditions, other radiolabeling strategies had to be developed to supply the need. Direct radiofluorination is either an inefficient method, and the use of bidirectional groups, or prosthetic groups, is needed to enable the binding between the radionuclide fluorine-18 and a peptide functionalized. New peptides radiolabeling strategies have been developed sourcing increase the synthesis yield, its chemoselectivity, and the binding stability, and reduce the total process time and the number of steps required. The progress of radiofluorination methodologies led to development of the amidation, acylation, imidation, and alkylation techniques, the use of thiol groups, photochemical conjugation, chemoselective reactions, and “click chemistry”, in addition to use of FDG molecule and heteroatoms as linkers. This paper presents the main strategies used for peptides radiofluorination, presenting their positive and negative points, and the prosthetic groups most used in each method.展开更多
While serious stability issues impede the commercialization of perovskite solar cells(PSCs),two-dime nsional(2D)perovskites based on fluorinated bulky cations have emerged as more intrinsically stable materials.Howeve...While serious stability issues impede the commercialization of perovskite solar cells(PSCs),two-dime nsional(2D)perovskites based on fluorinated bulky cations have emerged as more intrinsically stable materials.However,the influence of fluorination degree of the bulky aromatic cation on the per-formance of resulting PSCs has not been scrutinized.Here,2D perovskites(FxPEA)_(2)PbI_(4)(x=1,2,3,5)are grown in situ on the surface of the three-dime nsion al(3D)perovskite and dem on strate effective passivation of the surface defects of 3D perovskite.The power conversion efficiency(PCE)of the optimized devices were boosted from 20.75%for the control device to 21.09%,22.06%,22.74%and 21.86%for 2D/3D devices treated with 4-fluorophenethylamine iodide,3,5-difluorophenylethylamine iodide,2,4,5-trifluoroethylphenylethylamine iodide,and 1,2,3,4,5-pentafluorophenylethylamine iodide,respectively.We firstly reported two unexplored RP-type layered perovskites with F_(2)PEAI and F_(3)PEAI as bulky cations.The combined experimental and theoretical analysis revealed the reasons behind the various morphology,device performances,dynamic behavior,and humidity stability.The best performing F_(5)PEAI-treated device retaining 95.0%of its initial PCE under ambient atmosphere(with RH of 60%±5%)without encapsulation for 300 h storage.This work provides useful guidance for selecting fluorinated bulky cations with different molecular electronic properties,which will play an essential role in further improving the performance/stability of PSCs for the sake of further commercialization.展开更多
Hydrophobic interactions have been studied before in detail based on hydrophobic polymers,such as polystyrene(PS).Because fluorinated materials have relatively low surface energy,they often show both oleophobicity and...Hydrophobic interactions have been studied before in detail based on hydrophobic polymers,such as polystyrene(PS).Because fluorinated materials have relatively low surface energy,they often show both oleophobicity and hydrophobicity at the macroscopic level.However,it remains unknown how fluorination of hydrophobic polymer influences hydrophobicity at the microscopic level.We synthesized PS and fluorine-substituted PS(FPS)by employing the reversible addition-fragmentation chain transfer polymerization method.Contact angle measurements confirmed that FPS is more hydrophobic than PS at the macroscopic level due to the introduction of fluorine.However,single molecule force spectroscopy experiments showed that the forces required to unfold the PS and FPS nanoparticles in water are indistinguishable,indicating that the strength of the hydrophobic effect that drives the self-assembly of PS and FPS nanoparticles is the same at the microscopic level.The divergence of hydrophobic effect at the macroscopic and microscopic level may hint different underlying mechanisms:the hydrophobicity is dominated by the solvent hydration at the microscopic level and the surface-associated interaction at the macroscopic level.展开更多
The fluorination reaction involving aβ-ketosulfones by Selectfluor^(TM) was efficiently promoted by the ionic liquid,[Hbim]BF_4 (EL) as a reaction medium with methanol as co-solvent at room temperature under ultrason...The fluorination reaction involving aβ-ketosulfones by Selectfluor^(TM) was efficiently promoted by the ionic liquid,[Hbim]BF_4 (EL) as a reaction medium with methanol as co-solvent at room temperature under ultrasonic irradiation to afford the corresponding mono and difluoro-β-ketosulfones in excellent yields.The advantages of this method include among others the use of a recyclable, non-volatile ionic liquid,which promotes this protocol under room temperature without the requirement of any added catalyst under ultrasonic irradiation.展开更多
A new method for the separation and detection of trace metal impurities in cerium oxide （CeO2） using HPLC combined with electrothermal vaporization （ETV）-ICP-AES was developed. This combination links the high sepa...A new method for the separation and detection of trace metal impurities in cerium oxide （CeO2） using HPLC combined with electrothermal vaporization （ETV）-ICP-AES was developed. This combination links the high separation power of HPLC and high sensitivity of ETV-ICP-AES. The 2-ethylhexyl hydrogen 2-ethylhexylphosphate (P507) resin was used as stationary phase for the separation of metallic impurities in order to eliminate severe spectral interferences of the matrix. The dilute nitric acid was adopted as mobile phase for eluting Cu, Mn, Ni and La. The separation process can be accomplished in about 30 min. After concentrating the eluate by evaporation, the trace impurities were determined by using ETV-ICP-AES with the addition of 6% PTFE slurry as chemical modifier. The proposed method was applied to the analysis of CeO2 with satisfactory recoveries.展开更多
The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N’-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the con...The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N’-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.展开更多
Using PTFE as a chemical modifier, a method for the determination of trace impurities in high purity Nd2O3 by in-situ separation and electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry ...Using PTFE as a chemical modifier, a method for the determination of trace impurities in high purity Nd2O3 by in-situ separation and electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry （ETV-ICP-AES） was developed. The analyte-matrix separation and the temperature program of graphite furnace were investigated and optimized. The solid samples were directly introduced into graphite furnace in the form of slurry, where selective volatilization between the matrix and the analytes took place. The Nd matrix was retained in the graphite furnace during the evaporation step, while the trace analyte impurities were vaporized and removed. As a result, the matrix interference that is serious without the modifier is suppressed effectively. The achievable detection limits are (μg·g-1): Ti 0.15, Mn 0.15, Ni 0.20, Co 0.54, respectively. The proposed method was applied to direct determination of trace impurities in high purity Nd2O3 with satisfactory results.展开更多
基金Science Foundation for Distinguished Young Scholars in Tianjin,Grant/Award Number:19JCJQJC61700National Natural Science Foundation of China,Grant/Award Numbers:51773147,51973151,52130303National Key R&D Program of China,Grant/Award Number:2022YFB3805702。
文摘Lithium(Li)metal anodes have attracted extensive attention due to their ultrahigh theoretical capacity and low potential.However,the uneven deposition of Li near the unstable electrode/electrolyte interfaces leads to the growth of Li dendrites and the degradation of active electrodes.Herein,we directly fluorinate alkyne-containing conjugated microporous polymers(ACMPs)microspheres with fluorine gas(F_(2))to introduce a novel fluorinated interlayer as an interfacial stabilizer in lithium metal batteries.Using density functional theory methods,it is found that as-prepared fluorinated ACMP(FACMP)has abundant partially ionic C–F bonds.The C–F bonds with electrochemical lability yield remarkable lithiophilicity during cycling.The in situ reactions between the active C–F bonds and Li ions enable transfer of lithium fluoride microcrystals to the solid electrolyte interphase(SEI)layers,guaranteeing effective ionic distribution and smooth Li deposition.Consequently,Li metal electrodes with the fluorinated interlayers demonstrate excellent cycling performances in both half-batteries and full cells with a lithium bis(trifluoromethanesulfonyl)imide electrolyte as well as a nonfluorinated lithium bis(oxalate)borate electrolyte system.This strategy is highly significant in customizable SEI layers to stabilize electrode interfaces and ensure high utilization of Li metal anodes,especially in a nonfluorinated electrolyte.
基金supported by the National Key Research and Development Program of China(2020YFA0210701)the National Natural Science Foundation of China(22005134,12275119,U22A20439)+4 种基金the Shenzhen Science and Technology Program(RCBS20210609103647030)the Guangdong Basic and Applied Basic Research Foundation(2021A1515012403)the Shenzhen Science and Technology Program(KQTD20200820113047086)the Guangdong-Hong Kong-Macao Joint Laboratory for PhotonicThermal-Electrical Energy Materials and Devices(2019B121205001)the open research fund of Songshan Lake Materials Laboratory(2022SLABFK04)。
文摘The development of all-solid-state lithium batteries(ASSLBs)depends on exploiting solid-state electrolytes(SSEs)with high ionic conductivity and electrochemical stability.Fluorination is generally considered to be an effective strategy to improve the ionic conductivity and electrochemical stability of inorganic SSEs.Here,we report the partial fluorination of the chlo rine sites in an antiperovskite,by which the orthorhombic Li_(2)OHCl was transformed into cubic Li_(2)OHCl_(0.9)F_(0.1),resulting in a fourfold increase in ionic conductivity at 30℃.The ab initio molecular dynamics simulations suggest that both the crystal symmetry and the anions electronegativity influence the diffusion of Li+in the antiperovskite structure.Besides,from the perspective of experiments and calculations,it is confirmed that fluorination is a feasible method to improve the electrochemical stability of antiperovskite SSEs.The LiFePO_(4)|Li cell based on Li_(2)OHCl_(0.9)F_(0.1) is also assembled and exhibits stable cycle performance,which indicates that fluorination of antiperovskite SSEs is an effective way to produce high-performance SSEs for practical application of ASSLBs.
基金supported by National Key Research and Development Program under Grant No.2022YFB3607100Shenzhen Research Programs under Grant Nos.JCYJ20200109140601691,JCYJ20190808154803565,SGDX20201103095607022,SGDX20211123145404006,and GXWD20201231165807007-20200807025846001。
文摘As growing applications demand higher driving currents of oxide semiconductor thin-film transistors(TFTs),severe instabilities and even hard breakdown under high-current stress(HCS)become critical challenges.In this work,the triggering voltage of HCS-induced self-heating(SH)degradation is defined in the output characteristics of amorphous indium-galliumzinc oxide(a-IGZO)TFTs,and used to quantitatively evaluate the thermal generation process of channel donor defects.The fluorinated a-IGZO(a-IGZO:F)was adopted to effectively retard the triggering of the self-heating(SH)effect,and was supposed to originate from the less population of initial deep-state defects and a slower rate of thermal defect transition in a-IGZO:F.The proposed scheme noticeably enhances the high-current applications of oxide TFTs.
基金supported by the National Key R&D Program of China(2021YFB2401800)the National Natural Science Foundation of China(22179008,21875022)+2 种基金the Natural Science Foundation of Chongqing,China(cstc2020jcyj-msxmX0589,cstc2020jcyjmsxmX0654)the support from Beijing Institute of Technology Research Fund Program for Young Scholarsthe 4B7B beamlines radiation equipment of Beijing Synchrotron Radiation Facility(2021-BEPC-PT-005924,2021-BEPC-PT-005967)。
文摘Cation-disordered rocksalt oxides(DRX)have been identified as promising cathode materials for high energy density applications owing to their variable elemental composition and cationic-anionic redox activity.However,their practical implementation has been impeded by unwanted phenomena such as irrepressible transition metal migration/dissolution and O_(2)/CO_(2)evolution,which arise due to parasitic reactions and densification-degradation mechanisms during extended cycling.To address these issues,a micron-sized DRX cathode Li_(1.2)Ni_(1/3)Ti_(1/3)W_(2/15)O_(1.85)F_(0.15)(SLNTWOF)with F substitution and ultrathin LiF coating layer is developed by alcohols assisted sol-gel method.Within this fluorination-induced integrated structure design(FISD)strategy,in-situ F substitution modifies the activity/reversibility of the cationic-anionic redox reaction,while the ultrathin LiF coating and single-crystal structure synergistically mitigate the cathode/electrolyte parasitic reaction and densification-degradation mechanism.Attributed to the multiple modifications and size effect in the FISD strategy,the SLNTWOF sample exhibits reversible cationic-anionic redox chemistry with a meliorated reversible capacity of 290.3 mA h g^(-1)at 0.05C(1C=200 mA g^(-1)),improved cycling stability of 78.5%capacity retention after 50 cycles at 0.5 C,and modified rate capability of 102.8 mA h g^(-1)at 2 C.This work reveals that the synergistic effects between bulk structure modification,surface regulation,and engineering particle size can effectively modulate the distribution and evolution of cationic-anionic redox activities in DRX cathodes.
基金financialy supported by the State Key Program of National Natural Science Foundation of China(no.52130303)the National Natural Science Foundation of China(no.51773147 and 51973151)
文摘The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.
基金Supported by the Program for New Century Excellent Talents in Universities of China under Grant No NCET-09-0867
文摘Previous calculations show that the two-dimensional(2 D) silicon carbide(SiC) honeycomb structure is a structurally stable monolayer. Following this, we investigate the electronic properties of the hydrogen and fluorine functionalized SiC monolayer by first-principles calculations. Our results show that the functionalized monolayer becomes metallic after semi-hydrogenation or semi-fluorination, while the semiconducting properties are obtained by the full functionalization. Compared with the bare SiC monolayer, the band gap of the fully hydrogenated system is increased, in comparison with the decrease of the gap in the fully fluorinated case. As a result, the band gap can be tuned from 0.73 to 4.14 eV by the functionalization. In addition to the metal-semiconductor transition, hydrogenation and functionalization also realize a direct-indirect semiconducting transition in the 2 D SiC monolayer. These results provide theoretical guidance for design of photoelectric devices based on the SiC monolayer.
基金supported by National Natural Science Foundation of China (No. 51777076)the Self-topic Fund of the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources (No. LAPS2019-21)
文摘This work treats the Al_(2)O_(3)-ER sample surface using dielectric barrier discharge fluorination(DBDF),DBD silicon deposition(DBD-Si),atmospheric-pressure plasma jet fluorination(APPJ-F)and APPJ silicon deposition(APPJ-Si).By comparing the surface morphology,chemical components and electrical parameters,the diverse mechanisms of different plasma modification methods used to improve flashover performance are revealed.The results show that the flashover voltage of the DBDF samples is the largest(increased by 21.2%at most),while the APPJ-F method has the worst promotion effect.The flashover voltage of the APPJ-Si samples decreases sharply when treatment time exceeds 180 s,but the promotion effect outperforms the DBD-Si method during a short modified time.For the mechanism explanation,firstly,plasma fluorination improves the surface roughness and introduces shallow traps by etching the surface and grafting fluorine-containing groups,while plasma silicon deposition reduces the surface roughness and introduces a large number of shallow traps by coating Si Oxfilm.Furthermore,the reaction of the DBD method is more violent,while the homogeneity of the APPJ modification is better.These characteristics influence the effects of fluorination and silicon deposition.Finally,increasing the surface roughness and introducing shallow traps accelerates surface charge dissipation and inhibits flashover,but too many shallow traps greatly increase the dissipated rate and facilitate surface flashover instead.
基金the National Natural Science Foundation of China (Grant nos. 21401142, 51972233)the Natural Science Foundation of Shanghai (Grant no. 19ZR1459200) for funding and Recruitment Program of Global Youth Experts (1000 plan)+1 种基金supported by the Shanghai Science and Technology Commission (14DZ2261100)the Fundamental Research Funds for the Central Universities。
文摘Cr doped Ruddlesden-Popper compound Sr2 TiO4 has been successfully modified by fluorine to form a new compound Sr2 Ti(0.95) Cr(0.05) O3 F2. Structure analysis suggests two types of fluorine in the structure of this new compound, i.e. intralayer and interlayer F, which induce strong built-in electric field within this layered compound. The electric field stems from uneven distribution of F atoms on the two sides of perovskite layers therefore leads to charge disproportionation. DFT calculations suggest that this unique structural feature is highly beneficial for charge dissociations as it breaks the coplanar settlement of conduction band minimum and valence band maximum whilst maintains the 2 D charge transportation properties. This is clearly demonstrated by the superior photocatalytic activities of Sr2 Ti(0.95) Cr(0.05) O3 F2 for hydrogen production from water. Apparent quantum efficiency(AQE) as high as 1.16% at 420 ± 20 nm has been achieved which stands as the highest AQE reported on Sr2 TiO4 to date. Photoelectrochemical(PEC)analysis confirms improved charge separation conditions and prolonged charge lifetime.
基金the National Natural Science Foundation of China(No.21703021 and No.U1931104)the Natural Science Foundation of Chongqing,China(No.cstc2017jcyjAX0068 and No.cstc2018jcyjAX0050)+2 种基金Venture&Innovation Support Program for Chongqing Overseas Returns(No.cx2018064)Foundation of 100 Young Chongqing University(No.0220001104428)Fundamental Research Funds for the Central Universities(No.106112017CDJQJ228807 and No.2018CDQYHG0009).
文摘The ground state rotational spectrum of 2,3,6-trifluoropyridine has been investigated in the 2.0-20.0 GHz region by pulsed jet Fourier transform microwave spectroscopy.The experimental rotational constants are A=3134.4479(2)MHz,B=1346.79372(7)MHz,and C=941.99495(6)MHz.The transitions are so intense that rotational transitions of all mono13C and 15N isotopologues are measured in natural abundance.The semi-experimental equilibrium rotational constants of the 7 isotopologues were derived by taking account of the anharmonic vibrational corrections,which allowed a semi-experimental determination of the equilibrium structure of 2,3,6-trifluoropyridine.
文摘A novel hybrid process for surface fluorination of polymers is being introduced. The process is based on ultra violet (UV) laser radiation, which on the one hand forms radicals out of an atmosphere of a partially fluorinated benzene, and on the other hand activates a polymer surface in the areas where the UV radiation hits the surface. The radicals can react with the polymer surface, hence altering the surface energy. With this process, a fluorine content of over 30% on the surface of bulk polystyrene can be achieved, while the smallest possible structure size was smaller than 1 mm.
文摘Medical-grade poly(methyl methacrylate) (PMMA) is extensively employed in the fabrication of a variety of medical implants, including intraocular lenses (IOLs). However, a postoperative complication that leads to the failure of the implanted intraocular lenses has been recently identified. This process, termed calcification, occurs when calcium-containing deposits accumulate on the surface of the IOL. In this study direct gas fluorination was used to modify the surface of PMMA in an attempt to increase the service lifetime of the material in optical applications. PMMA discs exposed to a 20% fluorine/nitrogen gas mixture for 24 h were compared with untreated PMMA discs serving as control samples. Over time, both surface-fluorinated and untreated PMMA samples immersed in a simulated aqueous humour solution (SAHS) (pH 7.4, 35°C) were used to carry out in vitro studies. Attenuated total refractive Infrared spectroscopy (ATR-IR) Scanning electron microscopy (SEM), coupled with Energy dispersive X-ray analysis (EDX), showed that calcium-containing surface deposits were less abundant on surface-fluorinated PMMA compared with the control samples, indicating that the fluorinated surface was acting as a barrier to the deposits. Gravimetric analysis data showed that the decreased rate of diffusion compared with that of a control sample was due to the fluorinated surface.
文摘Peptides have an important role in organism and its high quantity present in tumors leading to development of radiolabeled peptides for tumor-specific imaging. Once the traditional methodologies used for radiofluorination do not work with peptides, due to their harsh conditions, other radiolabeling strategies had to be developed to supply the need. Direct radiofluorination is either an inefficient method, and the use of bidirectional groups, or prosthetic groups, is needed to enable the binding between the radionuclide fluorine-18 and a peptide functionalized. New peptides radiolabeling strategies have been developed sourcing increase the synthesis yield, its chemoselectivity, and the binding stability, and reduce the total process time and the number of steps required. The progress of radiofluorination methodologies led to development of the amidation, acylation, imidation, and alkylation techniques, the use of thiol groups, photochemical conjugation, chemoselective reactions, and “click chemistry”, in addition to use of FDG molecule and heteroatoms as linkers. This paper presents the main strategies used for peptides radiofluorination, presenting their positive and negative points, and the prosthetic groups most used in each method.
基金financial support from the National Natural Science Foundation of China (Grant No. 21975260)the financial support from the National Natural Science Foundation of China (Grant No. 22078241).
文摘While serious stability issues impede the commercialization of perovskite solar cells(PSCs),two-dime nsional(2D)perovskites based on fluorinated bulky cations have emerged as more intrinsically stable materials.However,the influence of fluorination degree of the bulky aromatic cation on the per-formance of resulting PSCs has not been scrutinized.Here,2D perovskites(FxPEA)_(2)PbI_(4)(x=1,2,3,5)are grown in situ on the surface of the three-dime nsion al(3D)perovskite and dem on strate effective passivation of the surface defects of 3D perovskite.The power conversion efficiency(PCE)of the optimized devices were boosted from 20.75%for the control device to 21.09%,22.06%,22.74%and 21.86%for 2D/3D devices treated with 4-fluorophenethylamine iodide,3,5-difluorophenylethylamine iodide,2,4,5-trifluoroethylphenylethylamine iodide,and 1,2,3,4,5-pentafluorophenylethylamine iodide,respectively.We firstly reported two unexplored RP-type layered perovskites with F_(2)PEAI and F_(3)PEAI as bulky cations.The combined experimental and theoretical analysis revealed the reasons behind the various morphology,device performances,dynamic behavior,and humidity stability.The best performing F_(5)PEAI-treated device retaining 95.0%of its initial PCE under ambient atmosphere(with RH of 60%±5%)without encapsulation for 300 h storage.This work provides useful guidance for selecting fluorinated bulky cations with different molecular electronic properties,which will play an essential role in further improving the performance/stability of PSCs for the sake of further commercialization.
基金supported by the National Key R&D Program of China(Grant No.2020YFA0908100)。
文摘Hydrophobic interactions have been studied before in detail based on hydrophobic polymers,such as polystyrene(PS).Because fluorinated materials have relatively low surface energy,they often show both oleophobicity and hydrophobicity at the macroscopic level.However,it remains unknown how fluorination of hydrophobic polymer influences hydrophobicity at the microscopic level.We synthesized PS and fluorine-substituted PS(FPS)by employing the reversible addition-fragmentation chain transfer polymerization method.Contact angle measurements confirmed that FPS is more hydrophobic than PS at the macroscopic level due to the introduction of fluorine.However,single molecule force spectroscopy experiments showed that the forces required to unfold the PS and FPS nanoparticles in water are indistinguishable,indicating that the strength of the hydrophobic effect that drives the self-assembly of PS and FPS nanoparticles is the same at the microscopic level.The divergence of hydrophobic effect at the macroscopic and microscopic level may hint different underlying mechanisms:the hydrophobicity is dominated by the solvent hydration at the microscopic level and the surface-associated interaction at the macroscopic level.
文摘The fluorination reaction involving aβ-ketosulfones by Selectfluor^(TM) was efficiently promoted by the ionic liquid,[Hbim]BF_4 (EL) as a reaction medium with methanol as co-solvent at room temperature under ultrasonic irradiation to afford the corresponding mono and difluoro-β-ketosulfones in excellent yields.The advantages of this method include among others the use of a recyclable, non-volatile ionic liquid,which promotes this protocol under room temperature without the requirement of any added catalyst under ultrasonic irradiation.
文摘A new method for the separation and detection of trace metal impurities in cerium oxide （CeO2） using HPLC combined with electrothermal vaporization （ETV）-ICP-AES was developed. This combination links the high separation power of HPLC and high sensitivity of ETV-ICP-AES. The 2-ethylhexyl hydrogen 2-ethylhexylphosphate (P507) resin was used as stationary phase for the separation of metallic impurities in order to eliminate severe spectral interferences of the matrix. The dilute nitric acid was adopted as mobile phase for eluting Cu, Mn, Ni and La. The separation process can be accomplished in about 30 min. After concentrating the eluate by evaporation, the trace impurities were determined by using ETV-ICP-AES with the addition of 6% PTFE slurry as chemical modifier. The proposed method was applied to the analysis of CeO2 with satisfactory recoveries.
文摘The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N’-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.
文摘Using PTFE as a chemical modifier, a method for the determination of trace impurities in high purity Nd2O3 by in-situ separation and electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry （ETV-ICP-AES） was developed. The analyte-matrix separation and the temperature program of graphite furnace were investigated and optimized. The solid samples were directly introduced into graphite furnace in the form of slurry, where selective volatilization between the matrix and the analytes took place. The Nd matrix was retained in the graphite furnace during the evaporation step, while the trace analyte impurities were vaporized and removed. As a result, the matrix interference that is serious without the modifier is suppressed effectively. The achievable detection limits are (μg·g-1): Ti 0.15, Mn 0.15, Ni 0.20, Co 0.54, respectively. The proposed method was applied to direct determination of trace impurities in high purity Nd2O3 with satisfactory results.
