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Rutile-structured high-entropy oxyfluorides:A platform for oxygen evolution catalysis
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作者 Shengliang Qi Kaixin Zhu +2 位作者 Ting Xu Weiguang Ma Xu Zong 《Journal of Energy Chemistry》 2025年第3期253-262,共10页
High-entropy(HE)design provides ample opportunities for accessing catalysts with unique physiochemical properties for advanced energy and environmental applications.Although a variety of multi-cationic high-entropy ma... High-entropy(HE)design provides ample opportunities for accessing catalysts with unique physiochemical properties for advanced energy and environmental applications.Although a variety of multi-cationic high-entropy materials(HEMs)have been identified,HEMs consisted of multiple cationic and anionic elements are still limited.Herein,we present the design and synthesis of a series of rutile-structured high-entropy oxy fluorides(HEOFs),including[RuO_(2)]_(x)[MgMnZnCoF_(2)]_(y),[MnO_(2)]_(x)[MgMnZnCoF_(2)]_(y),[MoO_(2)]_(x)[MgMnZnCoF_(2)]_(y),[SnO_(2)]_(x)[MgMnZnCoF_(2)]_(y)and[TiO_(2)]_(x)[MgMnZnCoF_(2)]_(y)(x:y=3:1,2:1,1:1).All the HEOFs are obtained through mechanochemical alloying rutile-structured oxide and fluoride precursors and the HEOFs inherit the crystal structures of the skeleton oxides.Moreover,the HEOFs exhibit enhanced electrocatalytic oxygen evolution reaction(OER)activity than the corresponding oneelement precursors.Typically,the best-performed HEOF[RuO_(2)]_(3)[MgMnZnCoF_(2)]_(1)catalyst requires an overpotential of 240 mV to achieve a current density of 10 mA cm^(-2),which is lower than RuO_(2)(291 mV),More impressively,the specific mass activity of[RuO_(2)]_(3)[MgMnZnCoF_(2)]_(1)is 537.1 A g_(Ru)^(-1)at1.55 V(vs RHE),which is ca.7.6 times that of RuO_(2)(70.5 A g_(Ru)^(-1)).The enhanced electrocata lytic OER performance obtained on[RuO_(2)]_(3)[MgMnZnCoF_(2)]_(1)is ascribed to the contribution of the different cationic and anionic elements that modulates the electronic structures of the pristine RuO_(2),which facilitates efficient OER kinetics.This work demonstrates the efficacy of high-entropy design towards approaching excellent catalysts for enhanced electrocatalysis. 展开更多
关键词 Rutile-structured High-entropy oxyfluorides MECHANOCHEMICAL Electrocatalyst Oxygen evolution reaction
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Synthesis,Crystal Structure,and Properties of Inorganic-organic Hybrid M(Ⅱ)-Nb(V) (M=Co,Cu) Oxyfluorides
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作者 胡冰 李建荣 黄小荥 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2011年第5期678-684,共7页
Two isostructural inorganic-organic hybrid M(II)–Nb(V) oxyfluorides, namely, M(H2O)2(pyz)NbOF5 (M=Co 1, Cu 2; pyz=pyrazine) have been hydrothermally synthesized and structurally characterized. Both compound... Two isostructural inorganic-organic hybrid M(II)–Nb(V) oxyfluorides, namely, M(H2O)2(pyz)NbOF5 (M=Co 1, Cu 2; pyz=pyrazine) have been hydrothermally synthesized and structurally characterized. Both compounds possess two-dimensional layer structure constructed by neutral M(H2O)2NbOF5 chains inter-connected via bridging pyrazine ligands. The structure is further extended into three-dimensional supramolecular architecture through inter-layer H-bonding interactions between the coordinated water molecules and fluorine ions. The luminescent properties and thermal stability of both compounds have been investigated. 展开更多
关键词 hybrid material OXYFLUORIDE NIOBATE crystal structure
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Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d^0 transition metal oxyfluorides 被引量:7
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作者 Junben Huang Siru Guo +2 位作者 Zhizhong Zhang Zhihua Yang Shilie Pan 《Science China Materials》 SCIE EI CSCD 2019年第12期1798-1806,共9页
Exploration of new infrared(IR) nonlinear optical(NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formida... Exploration of new infrared(IR) nonlinear optical(NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation(SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d^0 transition metal fluorooxofunctional groups for designing mid-IR NLO materials. By studying a series of d^0 transition metal oxyfluorides(TMOFs),the influences of fluorooxo-functional groups with different d^0 configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d^0 configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d^0 TMOFs exhibit wide band gaps(all the band gaps >3.0 e V), large birefringence Δn(> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d^0 TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap. 展开更多
关键词 infrared nonlinear optical materials second harm onicgeneration d^0 transition metal oxyfluorides fluorooxofunctionalgroups
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Enhancement of ultraviolet upconversion photoluminescence of Y_(7)O_(6)F_(9):Pr,Gd induced by Li^(+)codoping
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作者 Huaiyong Li Yang Sun +7 位作者 Jinfeng Zhang Ziyi Zhang Yangbo Wang Chengchao Hu Xufeng Zhou Shanshan Du Jigong Hao Wei Li 《Journal of Rare Earths》 2025年第4期684-690,I0002,共8页
Ultraviolet upconversion photoluminescence materials have great potential in various fields,but the improvement of the upconversion efficiency is challenging.Codoping of Li^(+)is considered as an effective strategy an... Ultraviolet upconversion photoluminescence materials have great potential in various fields,but the improvement of the upconversion efficiency is challenging.Codoping of Li^(+)is considered as an effective strategy and widely used to improve the photoluminescence properties of phosphors.In this paper,Li^(+)is introduced into a Y_(7)O_(6)F_(9):Pr^(3+),Gd^(3+)system.The effect of Li^(+)codoping on the phase purity,crystal structure,micro structure,downshifting and upconversion photo luminescence as well as the decay dynamic of the phosphors was studied.It is revealed that the overall photoluminescence efficiency and the energy transfer efficiency from pr^(3+)to Gd^(3+)are greatly promoted.The downshifting and upconversion photoluminescence increase by 2.58 and 10 times as 6 mol%of Li^(+)is codoped.The photo luminescence decay dynamic study shows that the ^(3)P_(0)state decays slower in the Li^(+)-containing phosphor than the Li^(+)-free one.The improvement of the photoluminescence properties is due to the increase of the crystallinity and the reduce of the quenching center. 展开更多
关键词 UPCONVERSION PHOTOLUMINESCENCE Li^(+)-codoping OXYFLUORIDE Gadolinium PRASEODYMIUM Rare earths
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Effect of alumina content and heat treatment on microstructure and upconversion emission of Er^(3+)ions in oxyfluoride glass-ceramics 被引量:3
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作者 Mohammad Hasan Imanieh Bijan Eftekhari Yekta +4 位作者 Vahak Marghussian Inocencio Rafael Martin Benenzuela Alberto Hernandez Creus Saeed Shakhesi Esmaeil Eslami 《Journal of Rare Earths》 SCIE EI CAS CSCD 2012年第12期1228-1234,共7页
The effect of alumina content and heat treatment temperature and time, on microstructure and Er3+ (0.5 mol.%) emission of oxyfluoride glass-ceramics were investigated in this research. Two values of 1.8 (SA1.8Er0.... The effect of alumina content and heat treatment temperature and time, on microstructure and Er3+ (0.5 mol.%) emission of oxyfluoride glass-ceramics were investigated in this research. Two values of 1.8 (SA1.8Er0.5) and 2.18 (SA2.18Er0.5) were selected in this research for SiO2/Al2O3 ratio. According to DTA results, precursor glasses were heat treated at 630, 660 and 690 ℃ for 4 h and some glasses were also heat treated at 630 ℃ for 48 and 72 h. The results indicated that alumina content had significant effect on phase separation and viscosity of the glasses. Therefore the size, size distribution, and volume concentration of nano CaF2 crystals which precipitated during the heat treatment depended on alumina content of the glass. Due to the much smaller size of the precipitated CaF2 crystals in the glasses of low alumina content, these samples maintained excellent transparency and had narrower crystal size distribution than the high alumina glasses. The crystal size was increased markedly with the temperature increasing from 630 to 690 ℃. On the other hand a slight increase was observed in the crystal size by raising the heat treatment time in both glasses. Results indicated that in low alumina content glass (SA2.18Er0.5) the size of CaF2 nanocrystals was controlled in one order of magnitude. The increase of heat treatment time and temperature led to the incorporation of Er3+ ions into CaF2 crystalline phase, increasing significantly the upconversion intensity. After heat treatment at 690 ℃for 4 h, atomic force microscope (AFM) revealed the development of small crystals with an average size of 80 and 30 nm in SA1.8Er0.5 and SA2.18Er0.5 samples, respectively. 展开更多
关键词 oxyfluorides glass-ceramic CaF2 nanocrystals SiO3/Al2O3 ratio rare earths
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Nanocrystals precipitation and up-conversion luminescence in Yb^(3+)-Tm^(3+) co-doped oxyfluoride glasses 被引量:13
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作者 邱建备 宋志国 《Journal of Rare Earths》 SCIE EI CAS CSCD 2008年第6期919-923,共5页
Rare earth ions doped oxyfluoride glass with composition of 28SiO2·22AlO1.5·40PbF2·10PbO·(4.8-x) GdFy0.1NdF3.xYbF3·0.1TmF3 (x=-0, 0.1, 0.2, 0.5, 1, 2, 3, 4 and 4.8) in molar ratio was deve... Rare earth ions doped oxyfluoride glass with composition of 28SiO2·22AlO1.5·40PbF2·10PbO·(4.8-x) GdFy0.1NdF3.xYbF3·0.1TmF3 (x=-0, 0.1, 0.2, 0.5, 1, 2, 3, 4 and 4.8) in molar ratio was developed. When the oxyfluoride glasses were heat-treated at the first crystallization temperature, the glasses gave transparent glass-ceramics in which rare earth containing fluorite-type nanocrystals of about 17.2 nm in diameter uniformly precipitated in the glass matrix. Compared with the glasses before heat treatment, the glass-ceramics exhibited very strong blue up-conversion luminescence under 800 nm light excitation. Rare earth containing nanocrystals were also space selectively precipitated upon laser irradiation in an oxyfluoride glass, the size of precipitated nanocrystals could be controlled by laser power and scan speed. The intensity of the blue up-conversion luminescence was strongly dependent on the precipitation of β-PbF2 nanocrystal and the YbF3 concentration. The reasons for the highly efficient Tm^3+ up-conversion luminescence after laser irradiation were discussed. 展开更多
关键词 oxyfluoride glass nanocrystal UP-CONVERSION laser irradiation rare earths
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Luminescent properties of Dy^3+/Eu^3+ doped fluorescent glass for white LED based on oxyfluoride matrix 被引量:10
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作者 Jingxi An Shuang Zhang +6 位作者 Ruiwang Liu Guangxu Hu Zhiwei Zhang Yiyu Qiu Yanyan Zhou Fanming Zeng Zhongmin Su 《Journal of Rare Earths》 SCIE EI CAS CSCD 2021年第1期26-32,I0002,共8页
Rare earth ion-doped fluorescent glass has become a hotspot due to its characteristics.This work shows that the prepared Dy^3+and Dy^3+/Eu^3+doped glasses have white light emission under ultraviolet excitation.There i... Rare earth ion-doped fluorescent glass has become a hotspot due to its characteristics.This work shows that the prepared Dy^3+and Dy^3+/Eu^3+doped glasses have white light emission under ultraviolet excitation.There is a higher yellow light/blue light(Y/B)value,indicating an increase in the covalentity of Dy-O,and decrease in the symmetry with the increasing concentration of dopants(Dy^3+).The correlated color temperature(CCT)can be effectively reduced by the red light emission of Eu^3+,and the order of influence of excitation wavelength on CCT is 395 nm>382 nm>365 nm.The delay curve demonstrates the energy transfer from Dy^3+to Eu^3+.The glass has the characteristics of anti-blue light damage and wide tunable color temperature,which illustrates that it has potential application in the field of white LED. 展开更多
关键词 Oxyfluoride glass Y/B intensity ratio Energy transfer Correlation color temperature Rare earths
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Preparation and luminescence properties of Eu^(3+) doped oxyfluoride borosilicate glass ceramics 被引量:4
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作者 李艳红 赵丽 +1 位作者 张永明 马晶 《Journal of Rare Earths》 SCIE EI CAS CSCD 2012年第12期1195-1198,共4页
Oxyfluoride borosilicate glass with the molar composition of 60SiO2-15B2O3- 15Na2O-8CaF2-2NaF-0.25Eu2O3 was synthesized lay a traditional glass melting method. Glass ceramics containing CaF2 nanocrystals were prepared... Oxyfluoride borosilicate glass with the molar composition of 60SiO2-15B2O3- 15Na2O-8CaF2-2NaF-0.25Eu2O3 was synthesized lay a traditional glass melting method. Glass ceramics containing CaF2 nanocrystals were prepared by heat treating the glass samples at a temperature in the range of 6204580 ℃. The results of X-ray diffraction (XRD) indicated that the average crystallite size and the lattice constant of CaF2 nanocrystals increased with the heat treatment temperature increasing. The luminescence spectra showed that the emission intensity of Eu3+ doped glass ceramics was stronger than that of the glass matrix, and increased with the heat treatment temperature increasing. The left edge of excitation band shifted to shorter wavelength in the glass ceramics. The local environments of Eu3+ ions in the glass and glass ceramics were different. 展开更多
关键词 OXYFLUORIDE glass ceramics LUMINESCENCE local environment rare earths
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Research on Up-Conversion Mechanism in Er^(3+)/Yb^(3+)-Codoped Oxyfluoride Glass 被引量:5
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作者 杨魁胜 薛汇丽 +4 位作者 乌日娜 阚甲强 王伟忠 曾斌 张希艳 《Journal of Rare Earths》 SCIE EI CAS CSCD 2006年第z2期175-178,共4页
Er3 +/Yb3 +-codoped oxyfluoride crystallite glass was prepared with melting technique. The compositions and the melting temperature and the annealing temperature of the rare earth-doped crystallite glass were studied ... Er3 +/Yb3 +-codoped oxyfluoride crystallite glass was prepared with melting technique. The compositions and the melting temperature and the annealing temperature of the rare earth-doped crystallite glass were studied in detail. The emission spectra of samples were measured with the Hitachi F-4500 fluorescent photometer pumped by 980 nm wavelength laser. The up-conversion luminescence mechanism was illuminated on the view of the photophysics. By measuring the relationship between luminescent intensity and pump power, it is confirmed that the emission peaks at 550 nm belong to two-photon process, while that at 665 nm belongs to three-photon process. Moreover, the distributions of crystalline were determined by SEM. 展开更多
关键词 Er3+ /Yb3+ UP-CONVERSION oxyfluoride glass rare earths
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Luminescent properties of Ce^(3+)-doped transparent oxyfluoride glass ceramics containing BaGdF_5 nanocrystals 被引量:4
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作者 王倩 欧阳绍业 +3 位作者 张为欢 杨斌 张约品 夏海平 《Journal of Rare Earths》 SCIE EI CAS CSCD 2015年第1期13-19,共7页
The transparent oxyfluoride glass ceramics containing Ba Gd F5 nanocrystals were prepared with a composition of 42 Si O2-12Na2O-16Al2O3-24 Ba F2-4Gd2O3-2Ce F3(mol.%) by thermal treatment technology. The typical DSC ... The transparent oxyfluoride glass ceramics containing Ba Gd F5 nanocrystals were prepared with a composition of 42 Si O2-12Na2O-16Al2O3-24 Ba F2-4Gd2O3-2Ce F3(mol.%) by thermal treatment technology. The typical DSC curve, X-ray diffraction(XRD) and transmission electron microscopy(TEM) patterns were measured. The transmission spectra and luminescent properties were investigated. The decay times of the Gd^3+ ions at 312 nm excited with 275 nm for the Ce^3+ ions doped glass and glass ceramics specimens and the energy transfer process between Gd^3+ ions and Ce^3+ ions were also studied. The XRD analysis and the TEM images confirmed the generation of the spherical Ba Gd F5 nanocrystals. Compared with the PG specimen, the intensity of the luminescence spectra of the glass ceramics specimens was apparently enhanced with the heat treatment temperature increasing, and a blue shift in the excitation spectra and the emission spectra of glass ceramics specimens was obviously observed. In the fluorescence decay curves of the Gd^3+ ions, it could be obviously observed that the fluorescent intensity decays in the Ce^3+ ions doped glass and glass ceramics specimens decreased rapidly with the increase of the heat treatment temperature. In addition, the energy transfer efficiency from Gd3+ions to Ce^3+ ions was also calculated. 展开更多
关键词 transparent oxyfluoride glass ceramics BaGdF5 nanocrystals luminescent properties energy transfer rare earths
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Role of Heavy Metal Ions in the Formation of Oxyfluoride Glasses and Glass Ceramics 被引量:3
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作者 Min Liu Lijuan Zhao +4 位作者 Yan Liu Zijian Lan Lifen Chang Yiming Li Hua Yu 《Journal of Materials Science & Technology》 SCIE EI CAS CSCD 2014年第12期1213-1216,共4页
In order to investigate the influence of different heavy metal ions on the formation of the oxyfluoride glasses and glass ceramics, samples with different Pb F2/Cd F2 ratios have been prepared by the melting quenching... In order to investigate the influence of different heavy metal ions on the formation of the oxyfluoride glasses and glass ceramics, samples with different Pb F2/Cd F2 ratios have been prepared by the melting quenching and thermal treatment method. The different effects of Pb2 tand Cd2ton the glass network structure are investigated by FTIR and Raman spectra. During the formation of glass network structure, Pb2 tprefers to break the Sie Oe Si bond and subsequently bond to F for charge compensation, and Cd2 tprefers to break the SieO eA l bond and is surrounded by O2. Pb2 tand F gather together and form the fluoride nanocrystals,while Cd2 tremains in oxide matrix after thermal treatment. Introduction of proper Cd F2 is important to adjust and control the glass network structure and crystallization process in the fabrication of the transparent glass ceramics. 展开更多
关键词 Pb Cd Glass network Oxyfluoride glass ceramics
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Intense upconversion luminescence of Er^(3+)/Yb^(3+) codoped oxyfluoride borosilicate glass ceramics containing Ba_2GdF_7 nanocrystals 被引量:3
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作者 赵士龙 徐时清 +1 位作者 邓德刚 樊先平 《Journal of Rare Earths》 SCIE EI CAS CSCD 2010年第6期903-906,共4页
Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated. Fluoride nanocrystals Ba2GdF7 were... Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated. Fluoride nanocrystals Ba2GdF7 were successfully precipitated in glass matrix, which was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) results. In comparison with the as-made precursor, significant enhancement of upconversion luminescence was observed in the Er3+/Yb3+ codoped oxyfluoride glass ceramics, which may be due to the variation of coordination environment around Er3+ and Yb3+ ions after crystallization. The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process, and that of the blue upconversion luminescence was a three-photon process. 展开更多
关键词 oxyfluoride glass ceramics Er3+/Yb3+codoped spectroscopic properties rare earths
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Spectroscopic investigations on Er^(3+)/Yb^(3+)-doped oxyfluoride glass ceramics containing YOF nanocrystals 被引量:3
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作者 郑飞 徐时清 +3 位作者 赵士龙 邓德刚 华有杰 王焕平 《Journal of Rare Earths》 SCIE EI CAS CSCD 2012年第2期137-141,共5页
Spectroscopic properties of Er3+/Yb3+-doped transparent oxyfluoride borosilicate glass ceramics containing YOF nanocrystals were systematically investigated. X-ray diffraction (XRD) confirmed the formation of YOF ... Spectroscopic properties of Er3+/Yb3+-doped transparent oxyfluoride borosilicate glass ceramics containing YOF nanocrystals were systematically investigated. X-ray diffraction (XRD) confirmed the formation of YOF nanocrystals in the glassy matrix. Based on the Judd-Ofelt theory, the intensity parameters Ωi (i=2, 4, 6), spontaneous emission probability, radiative lifetime, radiative quantum efficiency and the effective emission bandwidth were investigated. The upconversion luminescence intensity of Er3+ ions in the glass ceramics increased significantly with the increasing crystallization temperature. The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process, and the blue upconversion luminescence was a three-photon absorption process. 展开更多
关键词 oxyfluoride glass ceramics Er3+/Yb3+ codoped spectroscopic properties rare earths
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Spectroscopic Properties and Judd-Ofelt Theory Analysis of Er^(3+)-Doped Heavy Metal Oxyfluoride Silicate Glass 被引量:3
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作者 徐时清 杨中民 +3 位作者 戴世勋 张军杰 胡丽丽 姜中宏 《Journal of Rare Earths》 SCIE EI CAS CSCD 2004年第3期375-380,共6页
Er^(3+)-doped heavy metal oxyfluoride silicate glass was fabricated and characterized, and the absorption spectrum and fluorescence spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ω_t (t =2, ... Er^(3+)-doped heavy metal oxyfluoride silicate glass was fabricated and characterized, and the absorption spectrum and fluorescence spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ω_t (t =2, 4, 6), spontaneous transition probability, fluorescence branching ratio and radiative lifetime of each energy levels for Er^(3+) were calculated by Judd-Ofelt theory, and stimulated emission cross-section of (()~4I_(13/2))→(()~4I_(15/2)) transition was calculated by McCumber theory. The results show that fluorescence full width at half maximum and stimulated emission cross-section of Er^(3+)-doped heavy metal oxyfluoride silicate glass are broad and large, respectively. Compared with other host glasses, the gain bandwidth property of Er^(3+)-doped heavy metal oxyfluoride silicate glass is close to those of tellurite and bismuth glasses, and has advantage over those of silicate, phosphate and germante glasses. 展开更多
关键词 inorganic nonmetallic materials heavy metal oxyfluoride silicate glass Er^(3+) ion spectroscopic properties Judd-Ofelt theory rare earths
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Upconversion luminescence of Tm^3+/Yb^3+ codoped oxyfluoride glasses 被引量:2
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作者 段忠超 张军杰 +2 位作者 何冬兵 戴世勋 胡丽丽 《Chinese Physics B》 SCIE EI CAS CSCD 2006年第1期209-212,共4页
Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - (4.9 - x) AlF3(x=0, 0.5, 1.0, 1.5, 2.0) in tool fraction, Furthermore, the upconversion luminescence c... Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - (4.9 - x) AlF3(x=0, 0.5, 1.0, 1.5, 2.0) in tool fraction, Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and near infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm^3+: ^1D2 →^3F4, ^1G4 →^3H6, ^1G4 →^3F4, and ^3H4 →^3H6, respectively, are observed. Due to the sensitization of Yb^3+ ions, all the upconversion luminescence intensities are enhanced considerably with Yb^3+ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions. 展开更多
关键词 upconversion luminescence Tm^3+/yb^3+ codoped oxyfluoride glass
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Recycling rare earth from ultrafine NdFeB waste by capturing fluorine ions in wastewater and preparing them into nano-scale neodynium oxyfluoride 被引量:1
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作者 He Sun Tuoyao Wang +1 位作者 Chengxiang Li Yusheng Yang 《Journal of Rare Earths》 SCIE EI CAS CSCD 2022年第5期815-821,I0005,共8页
Ultrafine NdFeB waste is a relatively clean waste produced during NdFeB magnet processing.Fluorinecontaining wastewater is a common type of industrial wastewater,such as stainless steel pickling wastewater.In this wor... Ultrafine NdFeB waste is a relatively clean waste produced during NdFeB magnet processing.Fluorinecontaining wastewater is a common type of industrial wastewater,such as stainless steel pickling wastewater.In this work,rare earth element neodynium was recycled from ultrafine NdFeB waste by capturing fluorine ions in the fluorine-containing wastewater and prepared into neodynium oxyfluoride.The reaction process was investigated through UV-Vis-NIR,thermogravimetry/differential thermogravimetry(TG/DTG),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).The neodymium hydroxide in the ultrafine NdFeB waste reacted with fluorine ions to form Nd(OH)_(2) F,and Nd(OH)_(2) F was then transformed into neodymium oxyfluoride after decomposition.The formed neodymium oxyfluoride is found to be particles with rhombohedral structure and a particle size of around 50 nm.The reaction kinetics of forming Nd(OH)_(2) F was investigated.The reaction kinetic equation was established and the reaction activation energy was calculated.The effect of fluorine ion concentration on the reaction rate and products was evaluated.The results show that the reaction rate increases with the increase of fluorine ion concentration in the range of 0.01-1.5 mol/L,but it has little effect.In addition,the fluorine ion concentration affects the crystallinity of formed neodymium oxyfluoride.The recycling process not only realizes the sustainable utilization of rare earths,but also reduces the concentration of fluorine ions in the fluorine-containing wastewater,achieving two goals with one stone. 展开更多
关键词 RECYCLING Ultrafine NdFeB waste Capturing fluorine ions Neodymium oxyfluoride Rare earths
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Evolution of Er^(3+) Distribution in the Oxyfluoride Glass Ceramics with Heating 被引量:1
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作者 MA En CHEN Da-Qin HU Zhong-Jian LIU Feng HUANG Zi-Xiang BAO Feng WANG Yuan-Sheng 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2007年第3期303-308,共6页
The distribution characteristics of Er^3+ ions doped in the oxyfluoride glass ceramics containing LaF3 nanocrystals heat-treated at 650 ℃ for different durations were investigated. The results of the integral absor... The distribution characteristics of Er^3+ ions doped in the oxyfluoride glass ceramics containing LaF3 nanocrystals heat-treated at 650 ℃ for different durations were investigated. The results of the integral absorption cross-section analysis demonstrated that the partition fraction of Er^3+ in LaF3 nanocrystals increases with prolonging of heating time, The anomalous phenomena of Er^3+ emissions in the up-and the down-conversion fluorescence spectra are well explained based on the calculated results. 展开更多
关键词 oxyfluoride glass ceramics rare earth nanocrystal UP-CONVERSION integral absorption cross-section
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Molten salt synthesis of neodynium oxyfluoride in various fluoride media with different fluoride ion activities 被引量:1
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作者 Yusheng Yang Tuoyao Wang +2 位作者 Ran Zhao Shuyan Zhang Zengwu Zhao 《Journal of Rare Earths》 SCIE EI CAS CSCD 2022年第12期1935-1944,I0005,共11页
Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)an... Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance. 展开更多
关键词 Molten salt synthesis Neodynium oxyfluoride Molten fluorides Fluoride ion activity Rare earths
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Near-infrared Quantum Cutting in Pr^(3+)-Yb^(3+) Co-doped Oxyfluoride Glass Ceramics Containing CaF_2 Nanocrystals 被引量:1
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作者 章丽丽 XU Jie +2 位作者 胡一晨 CHEN Guorong WANG Zhongjian 《Journal of Wuhan University of Technology(Materials Science)》 SCIE EI CAS 2013年第3期455-459,共5页
The Pr3+-Yb3+ co-doped oxyfluoride glass-ceramics containing CaF2 nanocrystals were obtained by thermal treatment on the as-made glasses. The structure of fluoride nanocrystals was investigated. The light-emitting m... The Pr3+-Yb3+ co-doped oxyfluoride glass-ceramics containing CaF2 nanocrystals were obtained by thermal treatment on the as-made glasses. The structure of fluoride nanocrystals was investigated. The light-emitting mechanism of pr3+-yb3+ in the near infrared region was proposed and the fluorescence lifetime and quantum efficiency was calculated. The results indicate that the main phase in the oxyfluoride glass- ceramics is CaF2 nanocrystal sized at 30 nm. Energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) have proved the incorporation of Pr3+ and Yb3+ into CaF2 nanocrystal lattice, Near-infrared quantum cutting involving Yb3+ 980 nm and 1 015 tun (2F5/2→2F7/2) emission has been achieved upon the excitation of the 3P0 energy level of Pr3+ at 482 nm. The fluorescence lifetime decreases sharply and quantum efficiency increases with increasing Yb3+ concentration, and the optimal quantum efficiency reaches 191%. 展开更多
关键词 oxyfluoride glass ceramic nanocrystal fluorescence near-infrared quantum cutting
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Thermal and radiative characteristics of oxyfluoride glass singly doped with lanthanide ions 被引量:1
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作者 Barbara KLIMESZ Grazyna DOMINIAK-DZIK Witold RYBA-ROMANOWSKI 《Journal of Rare Earths》 SCIE EI CAS CSCD 2010年第6期893-898,共6页
Rare earths-doped oxyfluoride glasses based on germanium oxide and lead fluoride were prepared from commercial raw materials. The glasses with general composition of 50GeO2-(50-x-y)PbO-yPbF2-xLnF3 (Ln=Pr3+-Yb3+), cont... Rare earths-doped oxyfluoride glasses based on germanium oxide and lead fluoride were prepared from commercial raw materials. The glasses with general composition of 50GeO2-(50-x-y)PbO-yPbF2-xLnF3 (Ln=Pr3+-Yb3+), contained different concentrations of optically active dopants (x=0.2 mol.% and 2 mol.%) and PbF2 (y≤15 mol.%). The differential thermal analysis (DTA) was used to determine both thermal characteristic and thermal stability properties of the glasses in the function of the kind of dopant, its concentration, and a glass composition. Characteristic glass temperatures such as glass transition temperature (Tg), glass crystallization temperature (Tc) and temperature corresponding to the maximum of the crystallization rate (Tpc) were evaluated. On the basis of obtained results, the thermal stabilities of glasses under study were evaluated using various thermal stability criteria (Dietzel factor ?T, Saad-Poulain factors H’ and S). It was found that the increase in rare earth fluoride contents influenced thermal characteristics when the characteristic temperatures of the individual glass was shifted towards higher values. The effect of the PbF2 content and the kind of rare earth impurity on the glass stability was observed. Absorption spectra of lanthanide-doped glasses were measured at room temperature and used to determine the phenomenological intensity parameters Ωt and next, to estimate radiative properties of lanthanide ions in this matrix. Radiative transition probabilities of luminescent states of Ln3+, branching ratios and radiative lifetimes were determined. The variation of the Ωt along the lanthanide series was presented and discussed. 展开更多
关键词 oxyfluoride glasses rare earths DTA thermal stability of glasses radiative transition probabilities radiative lifetimes
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