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
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
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
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
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
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
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
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
A series of novel quaternary ammonium surfactants containing adamantane were designed and synthesized from 1-adamanta- necarboxylic acid. The structures of target surfactants were confirmed by 1H NMR, elements analysi...A series of novel quaternary ammonium surfactants containing adamantane were designed and synthesized from 1-adamanta- necarboxylic acid. The structures of target surfactants were confirmed by 1H NMR, elements analysis and FFIR. Surface properties of these surfactants were investigated. Due to the lipophilicity of adamantane, the critical micelle concentration （CMC） and C2o values of the synthesized quaternary ammonium surfactants are lower than that of conventional quaternary ammonium surfactants.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
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
Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants w...Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants were confirmed by 1H NMR, FTIR and elements analysis and the surface properties of these surfactants were also studied by surface tension measurements. These target surfactants exhibit much lower critical micelle concentrations （CMC） and higher efficiency in lowering the surface tension of water than typical surfactants.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
A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography （IC） with electrochemical pretreatment has been developed. The pretreatment was performed in a novel electrochemi...A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography （IC） with electrochemical pretreatment has been developed. The pretreatment was performed in a novel electrochemical oxidationneutralization device （EOND）, in which iodide of the sample was oxidized to iodate and the alkaline digestion sample solution was neutralized. Under the optimized conditions, the limits of detection （LOD, S/N = 3） were 2.5 μg/L for fluoride and 20 μg/L for iodate, respectively. The recoveries were in the range of 93-102% for fluoride and 86-98% for iodate.展开更多
A series of fluorine- and piperazine-containing 1,2,4-triazole thione derivatives were synthesized by the Mannich reaction of triazole intermediates with various substituted piperazines and formaldehyde in high yields...A series of fluorine- and piperazine-containing 1,2,4-triazole thione derivatives were synthesized by the Mannich reaction of triazole intermediates with various substituted piperazines and formaldehyde in high yields. Structures of title compounds were confirmed by melting points, IR,~1H NMR,^（13）C NMR and elemental analysis. The preliminary bioassays for 17 novel title compounds showed that several compounds have significant fungicidal activity against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cerealis at 50 mg/m L.展开更多
Influence of CaO on thermal decomposition of REFCO3 was studied. The results showed that CaO did not affect significantly the decomposition ratio of REFCO3. The XRD experiment showed that there was a great deal of CaF...Influence of CaO on thermal decomposition of REFCO3 was studied. The results showed that CaO did not affect significantly the decomposition ratio of REFCO3. The XRD experiment showed that there was a great deal of CaF2 in the masting production, the gas chromatographic analysis on the gas of REFCO3 decomposed, and the 70% content of fluorine in the gas of REFCO3 added 15% CaO was reduced. CaO could absorb the fluorine from the decomposition of REFCO3, and the environmental pollution of the fluorine was greatly alleviated,展开更多
A novel fluorinated polyurethane （FPU） with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol （PTMG-g-HFP） as a soft segment, 1,6-hexamethylene diisocyanate （HDI） or toluene d...A novel fluorinated polyurethane （FPU） with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol （PTMG-g-HFP） as a soft segment, 1,6-hexamethylene diisocyanate （HDI） or toluene diisocyanate （TD1） as a hard segment and 1,4-butanodiol （BDO） as a chain extender. FTIR, ^1H NMR, ^13C NMR and GPC were used to characterize the structure of the fluorinated polyurethane. Thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by TGA. XPS analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. The results showed the fluorine enrichment on the surface of FPU.展开更多
The extraction equilibrium of cerium(IV) and fluorine (I) from H2SO4 solution by Cyanex 923 is studied. The extraction mechanism of Ce(IV) and F(I) by Cyanex 923 is determined by the method of slope analysis. The resu...The extraction equilibrium of cerium(IV) and fluorine (I) from H2SO4 solution by Cyanex 923 is studied. The extraction mechanism of Ce(IV) and F(I) by Cyanex 923 is determined by the method of slope analysis. The results show that Cyanex 923 can extract HF as HF·L and Ce4+ together with HF as Ce(HF)(HSO4)2(SO4)·2L by which HF comes into the organic phase mainly when there is Ce4+ in the solution, where L is the extractant. Temperature does not affect the extraction. The IR spectra of purified Cyanex 923 saturated with Ce(IV) and HF are discussed.展开更多
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.
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.
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 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.
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support by the Major Program of Guangdong University of Technology (No.405095220)
文摘A series of novel quaternary ammonium surfactants containing adamantane were designed and synthesized from 1-adamanta- necarboxylic acid. The structures of target surfactants were confirmed by 1H NMR, elements analysis and FFIR. Surface properties of these surfactants were investigated. Due to the lipophilicity of adamantane, the critical micelle concentration （CMC） and C2o values of the synthesized quaternary ammonium surfactants are lower than that of conventional quaternary ammonium surfactants.
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financial support by the Key Program for Scientific and Technological Innovations of Higher Education Institutes in Guangdong Province(No.CXZD1022)
文摘Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants were confirmed by 1H NMR, FTIR and elements analysis and the surface properties of these surfactants were also studied by surface tension measurements. These target surfactants exhibit much lower critical micelle concentrations （CMC） and higher efficiency in lowering the surface tension of water than typical surfactants.
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.
文摘A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography （IC） with electrochemical pretreatment has been developed. The pretreatment was performed in a novel electrochemical oxidationneutralization device （EOND）, in which iodide of the sample was oxidized to iodate and the alkaline digestion sample solution was neutralized. Under the optimized conditions, the limits of detection （LOD, S/N = 3） were 2.5 μg/L for fluoride and 20 μg/L for iodate, respectively. The recoveries were in the range of 93-102% for fluoride and 86-98% for iodate.
基金supported by the National Natural Science Foundation of China (No. 21372133)‘‘111’’ Project of Ministry of Education of China (No. B06005)
文摘A series of fluorine- and piperazine-containing 1,2,4-triazole thione derivatives were synthesized by the Mannich reaction of triazole intermediates with various substituted piperazines and formaldehyde in high yields. Structures of title compounds were confirmed by melting points, IR,~1H NMR,^（13）C NMR and elemental analysis. The preliminary bioassays for 17 novel title compounds showed that several compounds have significant fungicidal activity against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cerealis at 50 mg/m L.
基金Project supported by the National Natural Science Foundation of China (50574031)
文摘Influence of CaO on thermal decomposition of REFCO3 was studied. The results showed that CaO did not affect significantly the decomposition ratio of REFCO3. The XRD experiment showed that there was a great deal of CaF2 in the masting production, the gas chromatographic analysis on the gas of REFCO3 decomposed, and the 70% content of fluorine in the gas of REFCO3 added 15% CaO was reduced. CaO could absorb the fluorine from the decomposition of REFCO3, and the environmental pollution of the fluorine was greatly alleviated,
基金Financial support from the Fundamental Research Foundation of Beijing Institute of Technology (No.20070442005)
文摘A novel fluorinated polyurethane （FPU） with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol （PTMG-g-HFP） as a soft segment, 1,6-hexamethylene diisocyanate （HDI） or toluene diisocyanate （TD1） as a hard segment and 1,4-butanodiol （BDO） as a chain extender. FTIR, ^1H NMR, ^13C NMR and GPC were used to characterize the structure of the fluorinated polyurethane. Thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by TGA. XPS analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. The results showed the fluorine enrichment on the surface of FPU.
基金the National Progeny entitled 'BasicResearch Of Rare Earths '(G1998061502) and the National Natural Science Foundationof Chi
文摘The extraction equilibrium of cerium(IV) and fluorine (I) from H2SO4 solution by Cyanex 923 is studied. The extraction mechanism of Ce(IV) and F(I) by Cyanex 923 is determined by the method of slope analysis. The results show that Cyanex 923 can extract HF as HF·L and Ce4+ together with HF as Ce(HF)(HSO4)2(SO4)·2L by which HF comes into the organic phase mainly when there is Ce4+ in the solution, where L is the extractant. Temperature does not affect the extraction. The IR spectra of purified Cyanex 923 saturated with Ce(IV) and HF are discussed.
