Fluorine(F)-enriched soils,resulting from geogenic processes or superimposed by anthropogenic activities,have raised significant concerns due to their phytotoxicity and potential threats to human health.Soils in centr...Fluorine(F)-enriched soils,resulting from geogenic processes or superimposed by anthropogenic activities,have raised significant concerns due to their phytotoxicity and potential threats to human health.Soils in central Guizhou Province exhibit F enrichment,with a mean F concentration of 1067 mg/kg.However,the associated human health risks and geochemical mechanisms driving F enrichment in these soils remain insufficiently understood.In areas with a natural geological background,the average concentrations of F in rice,vegetables,drinking water,and ambient air are 1.54 mg/kg,0.54 mg/kg,0.16 mg/L,and 0.29μg/m^(3),respectively.In contrast,samples collected near phosphorous chemical plants demonstrate elevated F concentrations:1.78 mg/kg in rice,1.53 mg/kg in vegetables,0.20 mg/L in drinking water,and 11.98μg/m^(3) in ambient air.Fluorine in soils was immobilized by apatite and clay minerals,and hardly transferred into water and crops.The fixation of F-by Ca^(2+)in water and by Fe/Al hydroxides and clay minerals in bottom sediment further reduces F concentrations in water.As a result,hazard quotient(HQ)values below 1.0 indicate negligible fluorine-related health risk in geological background regions.However,ambient air near phosphorous chemical plant exhibited a 41.3-fold increase in F concentration compared to geological background regions.Fluorine-laden emissions can be directly inhaled or deposited on vegetable leaves and orally ingested into human bodies.Improvement of F-rich waste gas disposal and restricted leafy vegetable cultivation are effective measures to reduce F health risks in phosphorous chemical plant regions.展开更多
Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of ...Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of dual-site doped Na_(3-2x)Sb_(1-x)W_(x)S_(4-x)F_(x)(x=0,0.12,0.24,0.36)electrolytes through high-energy ball milling followed by high-temperature sintering is prepared,where tungsten(W)substitutes for antimony(Sb)and fluorine(F)replaces sulfur(S)in the NSS lattice.The co-doping of W and F not only broadens the interplanar spacing of NSS but also promotes the stable formation of the cubic phase of NSS,thereby effectively enhancing the transport ability of sodium ions within NSS.Among them,Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24) exhibits the highest ionic conductivity of 4.45 mS·cm^(-1).Furthermore,F doping facilitates the in-situ formation of NaF between the electrolyte and metallic sodium,significantly improving interfacial stability.Electrochemical evaluation shows that the Na/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na symmetric cell achieves a high critical current density of 1.65 mA·cm^(-2) and maintains stable sodium plating/stripping cycling for 500 h at 0.1 mA·cm^(-2).Additionally,the TiS2/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na full cell exhibits outstanding cycling stability and rate capability.展开更多
Ferroelectrics(FEs)have shown great potential in sensors,actuators,and electrocaloric cooling due to their direct cross-couplings between electric polarization and mechanical,thermal,and dielectric properties[1−3]Comp...Ferroelectrics(FEs)have shown great potential in sensors,actuators,and electrocaloric cooling due to their direct cross-couplings between electric polarization and mechanical,thermal,and dielectric properties[1−3]Compared with oxide FEs,polymer FEs possess good flexible and shape adaptability,making them promising candidates for flexible electronics and biocompatible devices[4].展开更多
Several conjugate components represent the aquatic ecosystem of Lake Baikal:Baikal water(surface and deep water),groundwater from boreholes,water of numerous Baikal tributaries,cold and hot mineral springs around Lake...Several conjugate components represent the aquatic ecosystem of Lake Baikal:Baikal water(surface and deep water),groundwater from boreholes,water of numerous Baikal tributaries,cold and hot mineral springs around Lake Baikal,and the Angara River,the only runoff reflecting all this aquatic diversity.River waters in the Baikal region are known to be deficient in some vital elements,including fluorine.This article discusses the features of the fluorine distribution in the water from the conjugate components of the Baikal ecosystem.Fluorine ion concentrations in the water of the Baikal ecosystem was determined using the potentiometric method.The study represents the monitoring that was carried out between 1997 and 2022 years.We determine likely causes of high and low fluorine concentrations in the water from different components,propose and substantiate the fluorine sources,geological and geochemical model of its influx and distribution features in the water of the Baikal ecosystem.展开更多
Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the cla...Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.展开更多
Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we syste...Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we systematically investigated F-modified polymers(PBTA-PSF,PBDB-PSF)and their nonfluorinated counterparts(PBTA-PS,PBDB-PS)through simulations and experiments.We found that F atoms effectively lower the vibrational frequency of the molecular skeleton and suppress exciton–vibration coupling,thereby reducing the nonradiative decay rate.Moreover,introducing F atoms significantly decreases the reorganization energy for the S_(0)→S_(1) and S_(0)→cation transitions while increasing the reorganization energy for the S_(1)→S_(0) and cation→S_(0) transitions.These changes facilitate exciton dissociation and reduce the energy loss caused by dissociation and nonradiative recombination of excitons.Additionally,introducing F atoms into polymers enhances theπ–πstacking strength and the crystal coherence length in both neat and blended films,ultimately resulting in improvements in the power conversion efficiency of PBTA-PSF:L8-BO and PBDB-PSF:L8-BO are 16.51%and 17.59%,respectively.This study provides valuable insights for designing organic semiconductor materials to minimize energy loss and achieve a higher power conversion efficiency.展开更多
Proton ceramic fuel cell efficiently converts chemical energy into electrical energy,representing a pivotal component of future energy systems.However,its current performance is hindered by limitations in cathode and ...Proton ceramic fuel cell efficiently converts chemical energy into electrical energy,representing a pivotal component of future energy systems.However,its current performance is hindered by limitations in cathode and electrolyte materials,thereby impeding commercialization.Anion doping emerges as a promising strategy to enhance the electrochemical efficiency of perovskite-based cathodes and electrolytes.However,integrating this approach within a single-cell structure still requires further research.In this study,F-doped perovskite oxides BaCo_(0.4)Fe_(0.4)Zr_(0.1)Y_(0.1)O_(2.9-δ)F_(0.1)(BCFZYF)and BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(2.9-δ)F_(0.1)(BZCYYbF)were synthesized for use as the cathode and electrolyte,respectively,in proton ceramic fuel cells.Our findings demonstrate that F-doped perovskite oxides exhibit superior electrochemical performance and enhanced structural stability.Furthermore,doping both electrodes and electrolytes with F ions improves their interfacial compatibility.The cell configuration BCFZYF|BZCYYbF|Ni-BZCYYbF achieved a peak power density of 998 mW·cm^(−2)at 650℃using H_(2)as fuel,and it maintained stable operation for over 400 h at 550℃with a current density of 400 mA·cm^(−2).This research underscores an effective strategy for enhancing the performance and durability of proton ceramic fuel cells.展开更多
In this review, the methodologies for fluorine incorporation of 40 fluorine-containing agrochemicals that received an international standardization organization(ISO) name during the last decade are described.The predo...In this review, the methodologies for fluorine incorporation of 40 fluorine-containing agrochemicals that received an international standardization organization(ISO) name during the last decade are described.The predominant approach for fluorine introduction of these agrochemicals is to use a fluorine-containing building block. Here we present how the fluorine-containing building blocks are introduced into these agrochemicals. The synthetic methods of fluorine-containing building blocks that are not easily available are also specifically discussed. Fluoroarenes, difluomethylarenes and trifluomethylarenes are the main building blocks that have been used in this review. Fluorine-containing small molecules, such as alcohol,amine, ketoester, olefin are also widely used. The only example of late-stage fluorination is the synthesis of fungicide quinofumelin. We believe the fluorine introduction methods described here can provide ideas for the development of new and economical pesticide synthetic routes, and stimulate researchers to develop new fluorine incorporation methods and create new pesticides.展开更多
Bisphenol A dicyanate ester resins modified by fluorine-containing liquid crystal compound(LCFE)are applied as polymer matrix(LCFE-BADCy),poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers as rein-forcements,and fluorin...Bisphenol A dicyanate ester resins modified by fluorine-containing liquid crystal compound(LCFE)are applied as polymer matrix(LCFE-BADCy),poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers as rein-forcements,and fluorine/adamantane PBO precursor(pre FABPBO)as interfacial compatibilizer to prepare the corresponding PBO fibers/FABPBO/LCFE-BADCy wave-transparent laminated composites.LCFE could improve the order degree of BADCy cured network,in favor of enhancing the wave-transparent perfor-mance,mechanical properties,and intrinsic thermal conductivity.The dielectric constant and dielectric loss of PBO fibers/FABPBO/LCFE-BADCy composites are highly temperature(25–200℃)and frequency(10^(4)–10^(7) Hz and 8.2–12.4 GHz)stable with the value of 2.49 and 0.003 under 10^(6) Hz at 25℃,and the corresponding wave transmission efficiency is 95.0%,higher than that of 92.5%for PBO fibers/BADCy com-posites.The interlamellar shear strength and flexural strength are respectively 50.7 MPa and 682.5 MPa,38.1%and 16.2%higher than those of PBO fibers/BADCy composites.Besides,the volume resistivity,breakdown voltage,heat resistance index,glass transition temperature,flame retardant grade,and ul-timate oxygen index of PBO fibers/FABPBO/LCFE-BADCy composites are respectively 5.3×10^(15)Ωcm,29.75 kV/mm,217.2℃,245.7℃,V-1 grade,and 33.6%,expected to be performed as a new generation of“lightweight/loading/wave-transparent”electromagnetic window materials in advanced military weapons and civil communication base station.展开更多
The firing tests with clay blocks were undertaken to study thefluorine expulsion and retention char- acteristics of calcium-basedmaterials during the firing of brick clays. The results indicate thatfluorine expulsion ...The firing tests with clay blocks were undertaken to study thefluorine expulsion and retention char- acteristics of calcium-basedmaterials during the firing of brick clays. The results indicate thatfluorine expulsion begins at approx. 600-700 deg. C, and the mainportion occurs in 800-1000 deg. C. The mode of firing has someeffects on fluorine expulsion. Additives of calcium-based materialcan reduce fluorine expulsion, which is mainly attributed to theincreased formation of CaF_2 during clay firing. In addition, theoptimum addition tests of 6 calcium-based materials with higherefficiency were carried out in a brick kiln. More than 75/100fluorine is retained in the brick body and there is no adverse effecton brick product. This makes it possible for brickyard to achievenon-polluting production.展开更多
Tongshan area,a part of the floodplain of the abandoned Huanghe River, is one of the popular endemic fluorosis areas in East China. One of the reasons is high concentration of fluorine in shallow groundwater. Test res...Tongshan area,a part of the floodplain of the abandoned Huanghe River, is one of the popular endemic fluorosis areas in East China. One of the reasons is high concentration of fluorine in shallow groundwater. Test results of 36 groundwater samples show that fluorine concentration in shallow groundwater is 0.18–6.7 mg/L and 50 % of the samples exceed the Chinese drinking water quality standard. There exists a significant negative correlation in content between Ca2+ and F - . The correlations between fluorine concentration and other cations (for example Na+, K+, Mg2+) are not significant. The content of dissolved fluorine from the flooding sediments of the Huanghe River that varying from 5.6 mg/kg to 15.2 mg/kg plays an important role in forming the high fluorine groundwater. Usually, the dissolved fluorine content in silt is much higher than that in silty clay and clay. According to the geological investigation fluorine content in deep groundwater (over 60 m) is less than 1.0 mg/L and suitable for drinking, so it is an effective measure to prevent endemic fluorosis by extracting deep groundwater in disease areas.展开更多
A detailed comparison was done between the data about the F in coals published at home and abroad, and associated with the special situation in China. An introduction also was made to illuminate the forming, occurrenc...A detailed comparison was done between the data about the F in coals published at home and abroad, and associated with the special situation in China. An introduction also was made to illuminate the forming, occurrence and accumulation of the F in coals and its potential hazard to human and environment. Analytical data of coal samples were referred to study the great difference of the F content between coals and gangue. The results show that the average value of the F in the coal samples collected in different coalfields of China is 304x10^6, while that of gangue samples is surprisingly 1 319x10^6, especially the F content of coal ash from Bangmai in Yunnan Province reaches 4 800x10^6. It has been proved in many provinces of China that burning the coal and clay mixture can produce F contamination.展开更多
In order to determine the mechanism of bacterial tolerance to fluorine,Acidithiobacillus ferrooxidans ATCC 23270 was domesticated and studied under the conditions of different fluorine concentrations and pH values wit...In order to determine the mechanism of bacterial tolerance to fluorine,Acidithiobacillus ferrooxidans ATCC 23270 was domesticated and studied under the conditions of different fluorine concentrations and pH values with or without treatment by Proteinase K.The bacterial activities were observed through measuring the changes of solution potentials by platinum electrode with Ag/AgCl reference electrode and the intracellular fluorine was determined by-uorine ion-selective electrode.The results indicated that the tolerance of Acidithiobacillus ferrooxidans ATCC 23270 to fluorine could be obviously improved by domestication,HF was the effective form of fluorine to affect the bacterial activity,and pH increase or concentration change of ions of strong complex ability with fluorine ions in solution could result in false appearance of high fluorine-resistant strain.Some proteins located in cell wall or cell membrane were intimately relative with the bacterial fluorine tolerance.展开更多
The nitrogen and fluorine co doped TiO 2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetra butyl titanate with ammonium fluoride. Nitrogen and fluorine co doping causes the abso...The nitrogen and fluorine co doped TiO 2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetra butyl titanate with ammonium fluoride. Nitrogen and fluorine co doping causes the absorption edge of TiO 2 to shift to a lower energy region. The photocatalytic activity of co doped TiO 2 with anatase phases was found to be 2 4 times higher than that of the commercial TiO 2 photocatalyst Degussa P25 for phenol decomposition under visible light irradiation. The co doped TiO 2 powders only contain anatase phases even at 1000℃. Apparently, ammonium fluoride added retarded phase transformation of the TiO 2 powders from anatase to rutile. The substitutional fluorine and interstitial nitrogen atoms in co doped TiO 2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO 2 to shift to a lower energy region.展开更多
Siliconated polyurethane （Si-PU） was synthesized using isophorone diisocyanate （IPDI）, hydroxybutyl-terminated polydimethylsiloxane （PDMS）, polytetramethylene ether glycol （PTMG）, polypropylene glycol （PPG）,...Siliconated polyurethane （Si-PU） was synthesized using isophorone diisocyanate （IPDI）, hydroxybutyl-terminated polydimethylsiloxane （PDMS）, polytetramethylene ether glycol （PTMG）, polypropylene glycol （PPG）, 1,6-hexanediol （HDO）, dimethylol propionic acid （DMPA） and triethylamine （TEA）. Based on butyl acrylate （BA）, 2, 2, 2-trifluoroethylmethacrylate （TFEMA） and Si-PU as a seed emulsion, a novel core-shell type acrylic-polyurethane hybrid emulsion, containing siloxane and fluorine （F-Si-PU）, was prepared by seeded emulsion polymerization. The contents of siloxane and fluorine were determined according to the feed ratio. Fourier transform infrared spectroscopy （FTIR） was used to identify the chain structures of Si-PU and F-Si-PU. Investigation of transmission electron microscopy （TEM） confirmed the core-shell structure of F-Si-PU emulsion. Measurement results of water contact angle and the swelling ratio in water and n-octane for cured film showed that the water and the oil resistances for F-Si-PU had been significantly improved at a suitable content of fluorine and siloxane.展开更多
Ni-rich layered oxide LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(x≥0.8)is the most promising cathodes for future high energy automotive lithium-ion batteries.However,its application is hindered by the undesirable cycle stability,...Ni-rich layered oxide LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(x≥0.8)is the most promising cathodes for future high energy automotive lithium-ion batteries.However,its application is hindered by the undesirable cycle stability,mainly due to the irreversible structure change at high voltage.Herein,we demonstrate that F substitution with the appropriate amount(1 at%)is capable for improve the electrochemical performance of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cathode significantly.It is revealed that F substitution can reduce cation mixing,stabilize the crystal structure and improve Li transport kinetics.The resulted LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(1.99)F_(0.01)cathode can deliver a high capacity of 194.4 mAh g^(-1) with capacity retention of 95.5%after 100 cycles at 2 C and 165.2 mAh g^(-1) at 5 C.In-situ synchrotron X-ray technique proves that F ions in the cathode materials can suppress the irreversible phase transition from H2 phase to H3 phase in high voltage region by preventing oxygen gliding in a-b planes,ensuring a long-term cycle stability.展开更多
Tailoring the microstructure of pristine TiO2 is essential to narrow its band gap and prolong the charge lifetime. In particular, strategies involving fluorine have been used successfully to tune the surface chemistry...Tailoring the microstructure of pristine TiO2 is essential to narrow its band gap and prolong the charge lifetime. In particular, strategies involving fluorine have been used successfully to tune the surface chemistry, electronic structure, and morphology of TiO2 photocatalysts to improve their photocatalytic activity based on the strong complexation between fluoride ions and TiO2 and the high electronegativity of fluorine. In this review, we summarize the strategies involving fluorine to establish highly efficient TiO2 photocatalytic systems or fabricate highly efficient TiO2 photocatalysts. The main fluorine effects(i.e. the effects of fluorine on photocatalysis) include the following four aspects:(1) Surface effects of fluoride on TiO2 photocatalysis,(2) effects of fluorine doping on TiO2 photocatalysis,(3) fluoride-mediated tailoring of the morphology of TiO2 photocatalysts, and(4) the effects of fluorine on non-TiO2 photocatalysis. Additionally, the unique applications of these fluorine effects in photocatalysis, including selective degradation of pollutants, selective oxidation of chemicals, water-splitting to produce H2, reduction of CO2 to produce solar fuels, and improvement of the thermostability of TiO2 photocatalysts, are reviewed.展开更多
The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The uniq...The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The unique electronic effect and steric hindrance effect of fluorine substitutions make fluorine-containing polyimides occupy an important position in the transparent polyimide family.In this work,a series of transparent aromatic polyimides were prepared from a fixed 4,4’-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)and biphenyl diamines with different substitute groups at the 2,2’,6,6’-positions.We systematically studied the effects of pendant groups on the thermal,mechanical,optical and dielectric properties of these 6FDA-based polyimides with the aid of density function theory(DFT)calculation.In particular,we paid special attention to the simple but compact fluoro group substitution.The simple fluoro substitution brought the advantages of maintaining the linearity of the backbone and dense polymer chain packing,which would minimize the weakening of polyimides’inherent thermal,dimensional and mechanical properties.Comparing with trifluoromethyl substituted polyimides with the best optical transparency,polyimides containing fluoro substitutes exhibited slightly decreased optical transparency,but increased thermal and dimensional stability and higher mechanical strength.These results could shed light on the ultimate transparent polyimide film development toward the application in extreme working condition,e.g.,the colorless polyimide substrate film for the flexible display technology.展开更多
The different forms fluoine in different parts of molting process of krill was analyzed by culture of Antarctic krill (Euphausia superba). The results shaw that fluorine amount in cuticle is up to 90% of total in the ...The different forms fluoine in different parts of molting process of krill was analyzed by culture of Antarctic krill (Euphausia superba). The results shaw that fluorine amount in cuticle is up to 90% of total in the krill. During the krill molting process, the fluorine content in cuticle and muscle varies alternatively. This is to say, the fluorine content in new cuticle and muscle is much lower after molted, the fluorine in krill comes from seawater by biological absorption of the krill, and the fluorine absorbed by krill lost with the old cuticle at the end stage of molting process. Meanwhile, the new molting process starts again. The evidence is proved by the change of different forms fluorine content in cuticle and muscle during krill's molting process. At last the author proposes the fluorine enriching process model of Antarctic krill.展开更多
A novel compound of 9-[3-oxo-1-（4-bromopheny）-3-phenypropyl]fluorine （3） was synthesized via nucleophilic addition reaction under solvent-free condition. Its structure was determined by IR, 1H NMR, MS, elemental a...A novel compound of 9-[3-oxo-1-（4-bromopheny）-3-phenypropyl]fluorine （3） was synthesized via nucleophilic addition reaction under solvent-free condition. Its structure was determined by IR, 1H NMR, MS, elemental analysis and X-ray diffraction. The crystal of the new compound is of triclinic system, space group P-1 with a=9.7919（16）, b=11.0932（18）, c=11.2534（19） , α=76.927（3）, β=67.452（3）, γ=84.895（3）°, V=1099.7（3） 3, Z=2, Dc=1.369 g/cm3, μ=1.886 mm-1, F（000）=464, R=0.0586 and wR=0.1562 for 3145 observed reflections with Ⅰ 2σ（Ⅰ）. π-π Stacking interactions contribute to the stability of the structure.展开更多
基金supported by the projects of the China Geological Survey(DD20230543,DD20221770).
文摘Fluorine(F)-enriched soils,resulting from geogenic processes or superimposed by anthropogenic activities,have raised significant concerns due to their phytotoxicity and potential threats to human health.Soils in central Guizhou Province exhibit F enrichment,with a mean F concentration of 1067 mg/kg.However,the associated human health risks and geochemical mechanisms driving F enrichment in these soils remain insufficiently understood.In areas with a natural geological background,the average concentrations of F in rice,vegetables,drinking water,and ambient air are 1.54 mg/kg,0.54 mg/kg,0.16 mg/L,and 0.29μg/m^(3),respectively.In contrast,samples collected near phosphorous chemical plants demonstrate elevated F concentrations:1.78 mg/kg in rice,1.53 mg/kg in vegetables,0.20 mg/L in drinking water,and 11.98μg/m^(3) in ambient air.Fluorine in soils was immobilized by apatite and clay minerals,and hardly transferred into water and crops.The fixation of F-by Ca^(2+)in water and by Fe/Al hydroxides and clay minerals in bottom sediment further reduces F concentrations in water.As a result,hazard quotient(HQ)values below 1.0 indicate negligible fluorine-related health risk in geological background regions.However,ambient air near phosphorous chemical plant exhibited a 41.3-fold increase in F concentration compared to geological background regions.Fluorine-laden emissions can be directly inhaled or deposited on vegetable leaves and orally ingested into human bodies.Improvement of F-rich waste gas disposal and restricted leafy vegetable cultivation are effective measures to reduce F health risks in phosphorous chemical plant regions.
文摘Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of dual-site doped Na_(3-2x)Sb_(1-x)W_(x)S_(4-x)F_(x)(x=0,0.12,0.24,0.36)electrolytes through high-energy ball milling followed by high-temperature sintering is prepared,where tungsten(W)substitutes for antimony(Sb)and fluorine(F)replaces sulfur(S)in the NSS lattice.The co-doping of W and F not only broadens the interplanar spacing of NSS but also promotes the stable formation of the cubic phase of NSS,thereby effectively enhancing the transport ability of sodium ions within NSS.Among them,Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24) exhibits the highest ionic conductivity of 4.45 mS·cm^(-1).Furthermore,F doping facilitates the in-situ formation of NaF between the electrolyte and metallic sodium,significantly improving interfacial stability.Electrochemical evaluation shows that the Na/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na symmetric cell achieves a high critical current density of 1.65 mA·cm^(-2) and maintains stable sodium plating/stripping cycling for 500 h at 0.1 mA·cm^(-2).Additionally,the TiS2/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na full cell exhibits outstanding cycling stability and rate capability.
基金support from the Natural Science Fund for Colleges and Universities in Jiangsu Province(24KJB430029)the Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(NY224032,NY225006).
文摘Ferroelectrics(FEs)have shown great potential in sensors,actuators,and electrocaloric cooling due to their direct cross-couplings between electric polarization and mechanical,thermal,and dielectric properties[1−3]Compared with oxide FEs,polymer FEs possess good flexible and shape adaptability,making them promising candidates for flexible electronics and biocompatible devices[4].
基金the framework of the IGC SB RAS project(No.0284-2021-0003)supported by the RFFR ofi_m project(No.17-29-05022).
文摘Several conjugate components represent the aquatic ecosystem of Lake Baikal:Baikal water(surface and deep water),groundwater from boreholes,water of numerous Baikal tributaries,cold and hot mineral springs around Lake Baikal,and the Angara River,the only runoff reflecting all this aquatic diversity.River waters in the Baikal region are known to be deficient in some vital elements,including fluorine.This article discusses the features of the fluorine distribution in the water from the conjugate components of the Baikal ecosystem.Fluorine ion concentrations in the water of the Baikal ecosystem was determined using the potentiometric method.The study represents the monitoring that was carried out between 1997 and 2022 years.We determine likely causes of high and low fluorine concentrations in the water from different components,propose and substantiate the fluorine sources,geological and geochemical model of its influx and distribution features in the water of the Baikal ecosystem.
基金supported by National Natural Science Foundation of China(Nos.22201046,22371054)Local Innovation Research Team Project of Guangdong Pearl River Talent Plan(No.2017BT01Z032)。
文摘Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.
基金supported by the National Natural Science Foundation of China(Grant No.62027822)the National R&D Program of China(Grant No.2019YFA0706402).
文摘Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we systematically investigated F-modified polymers(PBTA-PSF,PBDB-PSF)and their nonfluorinated counterparts(PBTA-PS,PBDB-PS)through simulations and experiments.We found that F atoms effectively lower the vibrational frequency of the molecular skeleton and suppress exciton–vibration coupling,thereby reducing the nonradiative decay rate.Moreover,introducing F atoms significantly decreases the reorganization energy for the S_(0)→S_(1) and S_(0)→cation transitions while increasing the reorganization energy for the S_(1)→S_(0) and cation→S_(0) transitions.These changes facilitate exciton dissociation and reduce the energy loss caused by dissociation and nonradiative recombination of excitons.Additionally,introducing F atoms into polymers enhances theπ–πstacking strength and the crystal coherence length in both neat and blended films,ultimately resulting in improvements in the power conversion efficiency of PBTA-PSF:L8-BO and PBDB-PSF:L8-BO are 16.51%and 17.59%,respectively.This study provides valuable insights for designing organic semiconductor materials to minimize energy loss and achieve a higher power conversion efficiency.
基金supported by the National Natural Science Foundation of China(No.22278203)The authors appreciate the support of Zhejiang Zheneng Technology and Environment Group Co.,Ltd’s project(No.TD-KJ-23-005:Methanation of carbon monoxide coupled with in-situ formed hydrogen in a low-temperature SOEC reactor).
文摘Proton ceramic fuel cell efficiently converts chemical energy into electrical energy,representing a pivotal component of future energy systems.However,its current performance is hindered by limitations in cathode and electrolyte materials,thereby impeding commercialization.Anion doping emerges as a promising strategy to enhance the electrochemical efficiency of perovskite-based cathodes and electrolytes.However,integrating this approach within a single-cell structure still requires further research.In this study,F-doped perovskite oxides BaCo_(0.4)Fe_(0.4)Zr_(0.1)Y_(0.1)O_(2.9-δ)F_(0.1)(BCFZYF)and BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(2.9-δ)F_(0.1)(BZCYYbF)were synthesized for use as the cathode and electrolyte,respectively,in proton ceramic fuel cells.Our findings demonstrate that F-doped perovskite oxides exhibit superior electrochemical performance and enhanced structural stability.Furthermore,doping both electrodes and electrolytes with F ions improves their interfacial compatibility.The cell configuration BCFZYF|BZCYYbF|Ni-BZCYYbF achieved a peak power density of 998 mW·cm^(−2)at 650℃using H_(2)as fuel,and it maintained stable operation for over 400 h at 550℃with a current density of 400 mA·cm^(−2).This research underscores an effective strategy for enhancing the performance and durability of proton ceramic fuel cells.
基金National Natural Science Foundation of China (Nos.21732002,22077071)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206) for generous financial support for our programs。
文摘In this review, the methodologies for fluorine incorporation of 40 fluorine-containing agrochemicals that received an international standardization organization(ISO) name during the last decade are described.The predominant approach for fluorine introduction of these agrochemicals is to use a fluorine-containing building block. Here we present how the fluorine-containing building blocks are introduced into these agrochemicals. The synthetic methods of fluorine-containing building blocks that are not easily available are also specifically discussed. Fluoroarenes, difluomethylarenes and trifluomethylarenes are the main building blocks that have been used in this review. Fluorine-containing small molecules, such as alcohol,amine, ketoester, olefin are also widely used. The only example of late-stage fluorination is the synthesis of fungicide quinofumelin. We believe the fluorine introduction methods described here can provide ideas for the development of new and economical pesticide synthetic routes, and stimulate researchers to develop new fluorine incorporation methods and create new pesticides.
基金The authors are grateful for the support and funding from National Scientific Research Project(Basis Strengthening Plan)State Key Laboratory of Solidification Processing in NWPU(No.SKLSP202103).
文摘Bisphenol A dicyanate ester resins modified by fluorine-containing liquid crystal compound(LCFE)are applied as polymer matrix(LCFE-BADCy),poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers as rein-forcements,and fluorine/adamantane PBO precursor(pre FABPBO)as interfacial compatibilizer to prepare the corresponding PBO fibers/FABPBO/LCFE-BADCy wave-transparent laminated composites.LCFE could improve the order degree of BADCy cured network,in favor of enhancing the wave-transparent perfor-mance,mechanical properties,and intrinsic thermal conductivity.The dielectric constant and dielectric loss of PBO fibers/FABPBO/LCFE-BADCy composites are highly temperature(25–200℃)and frequency(10^(4)–10^(7) Hz and 8.2–12.4 GHz)stable with the value of 2.49 and 0.003 under 10^(6) Hz at 25℃,and the corresponding wave transmission efficiency is 95.0%,higher than that of 92.5%for PBO fibers/BADCy com-posites.The interlamellar shear strength and flexural strength are respectively 50.7 MPa and 682.5 MPa,38.1%and 16.2%higher than those of PBO fibers/BADCy composites.Besides,the volume resistivity,breakdown voltage,heat resistance index,glass transition temperature,flame retardant grade,and ul-timate oxygen index of PBO fibers/FABPBO/LCFE-BADCy composites are respectively 5.3×10^(15)Ωcm,29.75 kV/mm,217.2℃,245.7℃,V-1 grade,and 33.6%,expected to be performed as a new generation of“lightweight/loading/wave-transparent”electromagnetic window materials in advanced military weapons and civil communication base station.
文摘The firing tests with clay blocks were undertaken to study thefluorine expulsion and retention char- acteristics of calcium-basedmaterials during the firing of brick clays. The results indicate thatfluorine expulsion begins at approx. 600-700 deg. C, and the mainportion occurs in 800-1000 deg. C. The mode of firing has someeffects on fluorine expulsion. Additives of calcium-based materialcan reduce fluorine expulsion, which is mainly attributed to theincreased formation of CaF_2 during clay firing. In addition, theoptimum addition tests of 6 calcium-based materials with higherefficiency were carried out in a brick kiln. More than 75/100fluorine is retained in the brick body and there is no adverse effecton brick product. This makes it possible for brickyard to achievenon-polluting production.
基金Project 2001KJ11 supported by National investigation of land and resources
文摘Tongshan area,a part of the floodplain of the abandoned Huanghe River, is one of the popular endemic fluorosis areas in East China. One of the reasons is high concentration of fluorine in shallow groundwater. Test results of 36 groundwater samples show that fluorine concentration in shallow groundwater is 0.18–6.7 mg/L and 50 % of the samples exceed the Chinese drinking water quality standard. There exists a significant negative correlation in content between Ca2+ and F - . The correlations between fluorine concentration and other cations (for example Na+, K+, Mg2+) are not significant. The content of dissolved fluorine from the flooding sediments of the Huanghe River that varying from 5.6 mg/kg to 15.2 mg/kg plays an important role in forming the high fluorine groundwater. Usually, the dissolved fluorine content in silt is much higher than that in silty clay and clay. According to the geological investigation fluorine content in deep groundwater (over 60 m) is less than 1.0 mg/L and suitable for drinking, so it is an effective measure to prevent endemic fluorosis by extracting deep groundwater in disease areas.
基金"973 Program"(2006CB202202)The National Natural Science Foundation of China(40572090,40272124)
文摘A detailed comparison was done between the data about the F in coals published at home and abroad, and associated with the special situation in China. An introduction also was made to illuminate the forming, occurrence and accumulation of the F in coals and its potential hazard to human and environment. Analytical data of coal samples were referred to study the great difference of the F content between coals and gangue. The results show that the average value of the F in the coal samples collected in different coalfields of China is 304x10^6, while that of gangue samples is surprisingly 1 319x10^6, especially the F content of coal ash from Bangmai in Yunnan Province reaches 4 800x10^6. It has been proved in many provinces of China that burning the coal and clay mixture can produce F contamination.
基金Project(2010CB630903) supported by the National Basic Research Program of China
文摘In order to determine the mechanism of bacterial tolerance to fluorine,Acidithiobacillus ferrooxidans ATCC 23270 was domesticated and studied under the conditions of different fluorine concentrations and pH values with or without treatment by Proteinase K.The bacterial activities were observed through measuring the changes of solution potentials by platinum electrode with Ag/AgCl reference electrode and the intracellular fluorine was determined by-uorine ion-selective electrode.The results indicated that the tolerance of Acidithiobacillus ferrooxidans ATCC 23270 to fluorine could be obviously improved by domestication,HF was the effective form of fluorine to affect the bacterial activity,and pH increase or concentration change of ions of strong complex ability with fluorine ions in solution could result in false appearance of high fluorine-resistant strain.Some proteins located in cell wall or cell membrane were intimately relative with the bacterial fluorine tolerance.
文摘The nitrogen and fluorine co doped TiO 2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetra butyl titanate with ammonium fluoride. Nitrogen and fluorine co doping causes the absorption edge of TiO 2 to shift to a lower energy region. The photocatalytic activity of co doped TiO 2 with anatase phases was found to be 2 4 times higher than that of the commercial TiO 2 photocatalyst Degussa P25 for phenol decomposition under visible light irradiation. The co doped TiO 2 powders only contain anatase phases even at 1000℃. Apparently, ammonium fluoride added retarded phase transformation of the TiO 2 powders from anatase to rutile. The substitutional fluorine and interstitial nitrogen atoms in co doped TiO 2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO 2 to shift to a lower energy region.
基金Financial supports from the National Natural Science Foundation of China(No.50273035)Hangzhou Zhijiang Silicone Chemical Industry Co.,Ltd.are acknowledged.
文摘Siliconated polyurethane （Si-PU） was synthesized using isophorone diisocyanate （IPDI）, hydroxybutyl-terminated polydimethylsiloxane （PDMS）, polytetramethylene ether glycol （PTMG）, polypropylene glycol （PPG）, 1,6-hexanediol （HDO）, dimethylol propionic acid （DMPA） and triethylamine （TEA）. Based on butyl acrylate （BA）, 2, 2, 2-trifluoroethylmethacrylate （TFEMA） and Si-PU as a seed emulsion, a novel core-shell type acrylic-polyurethane hybrid emulsion, containing siloxane and fluorine （F-Si-PU）, was prepared by seeded emulsion polymerization. The contents of siloxane and fluorine were determined according to the feed ratio. Fourier transform infrared spectroscopy （FTIR） was used to identify the chain structures of Si-PU and F-Si-PU. Investigation of transmission electron microscopy （TEM） confirmed the core-shell structure of F-Si-PU emulsion. Measurement results of water contact angle and the swelling ratio in water and n-octane for cured film showed that the water and the oil resistances for F-Si-PU had been significantly improved at a suitable content of fluorine and siloxane.
基金financially supported by the National Natural Science Foundation of China(No.52071085,51671058)the Science and Technology Commission of Shanghai Municipality(No.19ZR1404200)。
文摘Ni-rich layered oxide LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(x≥0.8)is the most promising cathodes for future high energy automotive lithium-ion batteries.However,its application is hindered by the undesirable cycle stability,mainly due to the irreversible structure change at high voltage.Herein,we demonstrate that F substitution with the appropriate amount(1 at%)is capable for improve the electrochemical performance of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cathode significantly.It is revealed that F substitution can reduce cation mixing,stabilize the crystal structure and improve Li transport kinetics.The resulted LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(1.99)F_(0.01)cathode can deliver a high capacity of 194.4 mAh g^(-1) with capacity retention of 95.5%after 100 cycles at 2 C and 165.2 mAh g^(-1) at 5 C.In-situ synchrotron X-ray technique proves that F ions in the cathode materials can suppress the irreversible phase transition from H2 phase to H3 phase in high voltage region by preventing oxygen gliding in a-b planes,ensuring a long-term cycle stability.
文摘Tailoring the microstructure of pristine TiO2 is essential to narrow its band gap and prolong the charge lifetime. In particular, strategies involving fluorine have been used successfully to tune the surface chemistry, electronic structure, and morphology of TiO2 photocatalysts to improve their photocatalytic activity based on the strong complexation between fluoride ions and TiO2 and the high electronegativity of fluorine. In this review, we summarize the strategies involving fluorine to establish highly efficient TiO2 photocatalytic systems or fabricate highly efficient TiO2 photocatalysts. The main fluorine effects(i.e. the effects of fluorine on photocatalysis) include the following four aspects:(1) Surface effects of fluoride on TiO2 photocatalysis,(2) effects of fluorine doping on TiO2 photocatalysis,(3) fluoride-mediated tailoring of the morphology of TiO2 photocatalysts, and(4) the effects of fluorine on non-TiO2 photocatalysis. Additionally, the unique applications of these fluorine effects in photocatalysis, including selective degradation of pollutants, selective oxidation of chemicals, water-splitting to produce H2, reduction of CO2 to produce solar fuels, and improvement of the thermostability of TiO2 photocatalysts, are reviewed.
基金financially supported by the Key-Area Research and Development Program of Guangdong Province(No.2020B010182002)the Recruitment Program of Guangdong(No.2016ZT06C322)the Major Program of National Natural Science Foundation of China(No.51890871)。
文摘The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The unique electronic effect and steric hindrance effect of fluorine substitutions make fluorine-containing polyimides occupy an important position in the transparent polyimide family.In this work,a series of transparent aromatic polyimides were prepared from a fixed 4,4’-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)and biphenyl diamines with different substitute groups at the 2,2’,6,6’-positions.We systematically studied the effects of pendant groups on the thermal,mechanical,optical and dielectric properties of these 6FDA-based polyimides with the aid of density function theory(DFT)calculation.In particular,we paid special attention to the simple but compact fluoro group substitution.The simple fluoro substitution brought the advantages of maintaining the linearity of the backbone and dense polymer chain packing,which would minimize the weakening of polyimides’inherent thermal,dimensional and mechanical properties.Comparing with trifluoromethyl substituted polyimides with the best optical transparency,polyimides containing fluoro substitutes exhibited slightly decreased optical transparency,but increased thermal and dimensional stability and higher mechanical strength.These results could shed light on the ultimate transparent polyimide film development toward the application in extreme working condition,e.g.,the colorless polyimide substrate film for the flexible display technology.
基金National Natural Science Foundation of China under contract No. 0487013 and Office ofPolar Expedtion of China.
文摘The different forms fluoine in different parts of molting process of krill was analyzed by culture of Antarctic krill (Euphausia superba). The results shaw that fluorine amount in cuticle is up to 90% of total in the krill. During the krill molting process, the fluorine content in cuticle and muscle varies alternatively. This is to say, the fluorine content in new cuticle and muscle is much lower after molted, the fluorine in krill comes from seawater by biological absorption of the krill, and the fluorine absorbed by krill lost with the old cuticle at the end stage of molting process. Meanwhile, the new molting process starts again. The evidence is proved by the change of different forms fluorine content in cuticle and muscle during krill's molting process. At last the author proposes the fluorine enriching process model of Antarctic krill.
基金Supported by the Team Research for Excellent Mid-aged and Young Teachers of Higher Education of Hubei Province (T200707)
文摘A novel compound of 9-[3-oxo-1-（4-bromopheny）-3-phenypropyl]fluorine （3） was synthesized via nucleophilic addition reaction under solvent-free condition. Its structure was determined by IR, 1H NMR, MS, elemental analysis and X-ray diffraction. The crystal of the new compound is of triclinic system, space group P-1 with a=9.7919（16）, b=11.0932（18）, c=11.2534（19） , α=76.927（3）, β=67.452（3）, γ=84.895（3）°, V=1099.7（3） 3, Z=2, Dc=1.369 g/cm3, μ=1.886 mm-1, F（000）=464, R=0.0586 and wR=0.1562 for 3145 observed reflections with Ⅰ 2σ（Ⅰ）. π-π Stacking interactions contribute to the stability of the structure.
