We took Co_(0.2)Ni_(0.8)-MOF-74 with bimetallic synergistic effect as the basic material,and selected rare earth ions Ho,Gd,and Er with ion radii close to Co and Ni as the research objects for doping.The influence of ...We took Co_(0.2)Ni_(0.8)-MOF-74 with bimetallic synergistic effect as the basic material,and selected rare earth ions Ho,Gd,and Er with ion radii close to Co and Ni as the research objects for doping.The influence of rare earth ion doping amount and doping type on the eNRR performance of the catalyst was explored.The experimental results show that the ammonia yield rate and Faraday efficiency doped with Co_(0.2)Ni_(0.8)-MOF-0.5Ho are the highest,reaching 1.28×10^(-10)mol·s^(-1)·cm^(-2)/39.8%,which is higher than the1.12×10^(-10)mol·s^(-1)·cm^(-2)/32.2%of Co_(0.2)Ni_(0.8)-MOF-74,and is about 14.3%/23.7%higher than that without doping,respectively.And the stability of Co_(0.2)Ni_(0.8)-MOF-0.5 Ho is good(after 80 hours of continuous testing,the current density did not significantly decrease).This is mainly due to doping,which gives Co_(0.2)Ni_(0.8)-MOF-74 a larger specific surface area and catalytic active sites.The catalyst doped at the same time has more metal cation centers,which increases the electron density of the metal centers and enhances the corresponding eNRR performance.展开更多
Rare earth elements are indispensable raw materials for advanced aero-engines, special optical materials, and high-performance electronic products. With the development of the social economy, the global demand for rar...Rare earth elements are indispensable raw materials for advanced aero-engines, special optical materials, and high-performance electronic products. With the development of the social economy, the global demand for rare earth resources is increasing, and rare earths have become a key metal for the development of new industries and frontier technologies that are highly valued both at home and abroad. Ion-adsorbed rare earth ores are an important source of rare earths, so the efficient green leaching of ion-adsorbed rare earths is important. Researchers found that the selection of an efficient green leaching agent for ion-adsorbed rare earths is based on the zeta potential of tailing clay minerals in addition to leaching efficiency, and both zeta potential and leaching ion concentration are related to mineral acidity and alkalinity, and the pH of tailing water suspension is a direct indicator of environmental water quality requirements. Therefore, the efficiency of the leaching process is closely integrated with the environmental evaluation, and the characteristics and correlation of the changes in zeta potential, pH, conductivity and pollutant concentration of the pulp of clay mineral content during the leaching process of ore leaching and tailings aqueous electrolyte solution leaching are studied by evaluating the leaching system, and a set of correlation leaching efficiency and environmental impact evaluation method is established based on the results of the above analysis, which is of scientific development of ion adsorption rare earth resources. It has important theoretical significance and practical application value.展开更多
We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3+ or Sin^3+ into layer-s...We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3+ or Sin^3+ into layer-structured 10,12-pentacosadiynoic acid (PCDA) nanopar- ticles to obtain PCDA/rare earth ions nanocomposites (PCDA-RE) and subsequently annealing PCDA-RE at the temperature slightly higher than the melting point of pure PCDA crystals, followed by topochemically polymerizing the annealed PCDA-RE. The polymerized PCDA-RE, i.e. poly(10,12-pentacosadiynoic acid)/rare earth ions nanocomposites (PDARE: PDA-Dy or PDA-Sm), are largely reversible (PDA-Sm) or even completely reversible (PDA-Dy) in the thermochromism, while, without the doping, pure PDA is completely irreversible. It is confirmed that, PDA-RE are also layer-structured with a d-spacing of 5.4 nm, higher than the d-spacing of pure PDA (4.7 nm). In PDA-RE, the rare earth ions form a layer in-between and interact strongly with the PDA bilayers, being responsible for the high degree or even the complete reversibility. This is the first example to make PDA completely reversible through the doping of rare earth ions; the annealing process is essential for the complete reversibility since it removes any defects in the structure.展开更多
TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. Th...TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange (MO) in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4+ present the best activity to MO.展开更多
Ca1-xRxCu3Ti4O12(R=La,Y,Gd;x=0,0.1,0.2,0.3) electronic ceramics were fabricated by conventional solid-state reaction method.The microstructure and dielectric properties as well as impedance behavior were carefully inv...Ca1-xRxCu3Ti4O12(R=La,Y,Gd;x=0,0.1,0.2,0.3) electronic ceramics were fabricated by conventional solid-state reaction method.The microstructure and dielectric properties as well as impedance behavior were carefully investigated.XRD results showed that the secondary phases with the general formula R2Ti2O7 existed at grain boundaries of rare earth doped ceramics,which inhibited abnormal grain growth.The dielectric constant decreased from 4×105 in pure CaCu3Ti4O12(CCTO) ceramics to 2×103 with rare earth doping....展开更多
Materials with function of producing negative ions effection,containing valency-variable rare earth elements and semiconductor oxide,were fabricated.Free radicals produced by the materials were tested.The result shows...Materials with function of producing negative ions effection,containing valency-variable rare earth elements and semiconductor oxide,were fabricated.Free radicals produced by the materials were tested.The result shows that the materials can produce quite a few free radicals as·O^-_2 no matter whether they are under illumination of ultraviolet radiation or under visible light radiation,or under no light radiation, demonstrating semiconductor oxide can be catalysed under the visible light radiation.At the same time the result shows there is direct relation between the number of free radicals and of the negative ion produced by the materials,which meant that during photo-catalyzed and redox process of valency-variable rare earth elements free radicals translate into negative ions. A circular model is presented involving circulating change of valency-variable rare earth elements and water and oxygen absorbed on the surface of materials under the condition of photocatalysis.展开更多
Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been...Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been developed to analyze the concentration of rare earth ions using a smartphone camera. The success of this protocol relies on mesoporous silica nanoparticles(MSNs) with large-area negatively charged surfaces, on which the rare earth cations(e.g., Eu^(3+)) are efficiently adsorbed through electrostatic attraction to enable a ‘‘concentrating effect''. The initial adsorption rate is as fast as 4025 mg(g min)^(-1), and the adsorption capacity of Eu^(3+)ions in the MSNs is as high as 4730 mg g^(-1)(equivalent to ~41.2 M) at 70 °C. The concentrated Eu^(3+)ions in the MSNs can form a complex with a light sensitizer of 1,10-phenanthroline to significantly enhance the characteristic red emission of Eu^(3+)ions due to an ‘‘antenna effect'' that relies on the efficient energy transfer from the light sensitizer to the Eu^(3+)ions.The positive synergy of ‘‘concentrating effect'' and ‘‘antenna effect'' in the MSNs enables the analysis of rare earth ions in a wide dynamic range and with a detection limit down to ~80 nM even using a smartphone camera. Our results highlight the promise of the protocol in fieldwork for exploring valuable rare earth resources.展开更多
Nano-sized powders of rare-earth ions added CdFe2O4 ferrites were synthesized by oxalate co-precipitation method.The influence of R ions(R = Sm3+, Y3+, and La3+) on the microstructure and magnetic properties of C...Nano-sized powders of rare-earth ions added CdFe2O4 ferrites were synthesized by oxalate co-precipitation method.The influence of R ions(R = Sm3+, Y3+, and La3+) on the microstructure and magnetic properties of CdFe2O4 ferrites was studied.XRD, SEM, FTIR, and magnetic hysteresis loops were used for analyzing the samples.The addition of R ions alters the structure of the powders and decreases the crystalline size, lattice constant, and grain size.The magnetic properties such as saturation magnetization, remanent magnetization, and magnetic moment increased due to addition of rare-earth ions in CdFe2O4 ferrite.The formation of secondary phase on the grain boundaries supports the abnormal growth.FTIR spectra show two absorption bands.Results suggest that the magnetic properties depend on the particular method of preparation and additives.展开更多
Coupled with a petrographical study, I carried out an ion probe study of rare earth element microdistributions in mineral phases of silicate inclusions from the Colomera ⅡE iron meteorite. Most mineral grains have ho...Coupled with a petrographical study, I carried out an ion probe study of rare earth element microdistributions in mineral phases of silicate inclusions from the Colomera ⅡE iron meteorite. Most mineral grains have homogeneous REEs, but show considerable inter-grain variations by a factor of 2 to 100. The whole rock REE abundances for Colomera, estimated by combining REE data with modal abundances, are relatively LREE-enriched with REEs of -10'CI, which suggest that Colomera silicates were highly differentiated and might represent a low degree partial melt (-10%) of a chondritic source. REE geochemistry of Colomera silicate inclusions points to an origin that involves differentiation, dynamic mixing, remelting, reduction, recrystallization, and subsequent rapid cooling near the surface of a planetary body.展开更多
Pervaporation separation of water-acetic acid mixtures through Poly(AN-co-AA) membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigated for the first time. The results showed that the treatm...Pervaporation separation of water-acetic acid mixtures through Poly(AN-co-AA) membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigated for the first time. The results showed that the treatment with rare earth metal ions could greatly improve the characteristics of the separation of water-acetic acid mixtures.展开更多
Well-ordered metal structures, i.e. arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used. These arrays were prepared by the metal evap...Well-ordered metal structures, i.e. arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used. These arrays were prepared by the metal evaporation on track membranes. Calculations of reso- nanee frequencies of tips regarded as semispheroids were done taking into account the interaction between dipoles of tips. They were used to discuss experimental results for media with Eu(NO3)3·6H2O salt basing on data for bulk silver dielectric function.展开更多
The limitation of the random walk theory of energy transfer between rare earth ions in crystals published in literatures is pointed out in this paper. A modified model, which can be used in any level of rare earth ion...The limitation of the random walk theory of energy transfer between rare earth ions in crystals published in literatures is pointed out in this paper. A modified model, which can be used in any level of rare earth ion concentration when the interaction between donor and acceptor is different from that between donors, is introduced. measured fluorescence lifetimes of Yb^3+:YAl3(BO3)4 This model has been applied to analyze the with a series of Yb^3+ concentrations.展开更多
The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to ex...The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er(0.5)Yb(9.5):FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.展开更多
In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond d...In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.展开更多
Improving the up-conversion luminescence efficiency crucial in several related application areas. In this work, of rare-earth ions via the multi-photon absorption process is we theoretically propose a feasible scheme ...Improving the up-conversion luminescence efficiency crucial in several related application areas. In this work, of rare-earth ions via the multi-photon absorption process is we theoretically propose a feasible scheme to enhance the resonance-mediated two-photon absorption in Er3+ ions by shaping the femtosecond laser field with a rectangle phase modulation. Our theoretical results show that the resonance-mediated two-photon absorption can be decomposed into the on-resonant and near-resonant parts, and the on-resonant part mainly comes from the contribution of laser central frequency components, while the near-resonant part mainly results from the excitation of low and high laser frequency components. So, the rectangle phase modulation can induce a constructive interference between the two parts by properly designing the modulation depth and width, and finally realizes the resonance-mediated two-photon absorption enhancement. More- over, our results also show that the enhancement efficiency of resonance-mediated two-photon absorption depends on the laser pulse width (or laser spectral bandwidth), final state transition frequency, and intermediate and final state absorption bandwidths. The enhancement efficiency modulation can be attributed to the relative weight manipulation of on-resonant and near-resonant two-photon absorption in the whole excitation process. This study presents a clear physical insight for the quantum control of resonance-mediated two-photon absorption in the rare-earth ions, and there will be an important significance for improving the up-conversion luminescence efficiency of rare-earth ions.展开更多
TiO_2 sols modified by rare earth (RE) ions (Ce^(4+), Eu^(3+), or Nd^(3+))were prepared by coprecipitation-peptization method. The photocatalysis activity was studied byinvestigating the photodegradation effects of ac...TiO_2 sols modified by rare earth (RE) ions (Ce^(4+), Eu^(3+), or Nd^(3+))were prepared by coprecipitation-peptization method. The photocatalysis activity was studied byinvestigating the photodegradation effects of active brilliant red dye X-3B. It is found that TiO_2sols modified by Ce^(4+), Eu^(3+), or Nd^(3+) have the anatase crystalline structure, which areprepared at 70℃. All RE^(n+)-TiO_2 sol samples have uniform nanoparticles with similar morphology,which are homogenously distributed in aqueous colloidal systems. The particle sizes are 10, 8, and12 nm for Nd^(3+)-TiO_2, Eu^(3+)-TiO_2, and Ce^(4+)-TiO_2, respectively. The character of ultrafineand positive charge sol particles contributes to the good adsorption of X-3B dye molecule on thesurface of titania (about 30% X-3B adsorption amount). Experimental results exhibit thatRE^(n+)-TiO_2 sol photocatalysts have the capability to photodegrade X-3B under visible lightirradiation. Nd^(3+)-TiO_2 and Eu^(3+)-TiO_2 show higher photocatalytic activity than Ce^(4+)-TiO_2,which is due to the difference of standard redox potential of RE^(n+)/RE^((n-1)+). RE^(n+)-TiO_2sols demonstrate more excellent interfacial adsorption and photodegradation effects to X-3B thanP_(25) TiO_2 crystallites. Moreover, the degradation mechanism of X-3B is proposed as dyephotosensitization and electron scavenging by rare earth ions.展开更多
TiN coatings were deposited on polished substrates of W18Cr4V high speed steel by means of vacuum arc ion plating. The effect of cerium on adhesion between TiN coating and substrate was studied. The microstructures an...TiN coatings were deposited on polished substrates of W18Cr4V high speed steel by means of vacuum arc ion plating. The effect of cerium on adhesion between TiN coating and substrate was studied. The microstructures and composition of TiN coatings were also investigated by means of scanning electron microscope (SEM), Auger electron spectroscopy (AES), and X ray diffraction (XRD) technique. It was found that cerium is an effective modifying agent and the addition of suitable amount of cerium to TiN coatings can produce relatively excellent properties such as micro hardness, wear resistance, oxidation resistance and porosity. The experimental results show that the added cerium in TiN coatings makes a contribution to form the preferred direction along with a (111) or (222) close packed face, which may be one of the reasons that improves some properties mentioned above.展开更多
Ce (Ⅳ) nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine (PVP) and quatemized PVP incorporated into porous silica matrix. The effect of nitric acid concentration (0.5~6 mol...Ce (Ⅳ) nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine (PVP) and quatemized PVP incorporated into porous silica matrix. The effect of nitric acid concentration (0.5~6 mol·L^-1) and temperature (278 ~318 K) on Ce( Ⅳ ) sorption efficiency was investigated. Sorption increased with increasing nitric acid concentration, indicating that [Ce(NO3)6]^2- complex is the main adsorbed Ce(Ⅳ) species. Oxidation of sorbents by adsorbed Ce ( Ⅳ ) species resulting in Ce ( Ⅲ ) release to the solution was observed. Pyridine based anion exchangers exhibited higher oxidation stability compared to the commercial strong base anion exchanger. Ce( Ⅳ ) reduction was temperature dependent and obeyed pseudo-first-order reaction kinetics. Column separation of Ce ( Ⅳ ) from La ( Ⅲ ) and Y ( Ⅲ ) was carried out from 6 mol·L^-1 nitric acid with PVP based anion exchanger. Reasonable Ce (Ⅳ) breakthrough capacity (0.7 mol·kg^-1 PVP) was achieved. No remarkable decrease of capacity was observed within 3 consequent runs. In contrast, Ce (Ⅲ) leakage due to reduction decreased and breakthrough capacity slightly increased. This effect was more pronounced with increasing temperature. Regeneration with 0.1 mol·L^- 1 nitric acid was successful (recovery 100% ± 4% ) and Ce solution of high purity ( 〉 99.97% ) with respect to La and Y content was gained.展开更多
Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of t...Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).展开更多
The ion exchange model of the leaching process was determined via batch leaching experiments using the Kerr model, with the selectivity coefficient experimentally determined to be 12.59×10^-10 L^2/g^2. Solute tra...The ion exchange model of the leaching process was determined via batch leaching experiments using the Kerr model, with the selectivity coefficient experimentally determined to be 12.59×10^-10 L^2/g^2. Solute transport laws of ammonium ions (NH4 +) and rare earth ions (RE^3+) in column leaching were described by the convection-dispersion equation (CDE). The source and sink in the CDE were determined by the Kerr model. The CDE with strong nonlinearity was solved using the sequential non-iterative method. Compared with the breakthrough curve of RE^3+, the correlation coefficient between the simulated and experimental curves reached 0.8724. Therefore, this method can simulate the one-dimensional column leaching of weathered crust elution-deposited rare earth ore. Moreover, the effects of different concentrations of ammonium sulfate ((NH4)2SO4) solution on the leaching rate of rare earth were analyzed. The optimal concentration of the (NH4)2SO4 solution had a linear relationship with the rare earth grade.展开更多
基金Funded by the Central Government Guides Local Funds for Scientific and Technological Development(No.2023ZYQ004)the Hunan Provincial Natural Science Foundation of China(No.2021JJ50036)the Hunan Provincial Key Research and Development Plan(No.2023GK2083)。
文摘We took Co_(0.2)Ni_(0.8)-MOF-74 with bimetallic synergistic effect as the basic material,and selected rare earth ions Ho,Gd,and Er with ion radii close to Co and Ni as the research objects for doping.The influence of rare earth ion doping amount and doping type on the eNRR performance of the catalyst was explored.The experimental results show that the ammonia yield rate and Faraday efficiency doped with Co_(0.2)Ni_(0.8)-MOF-0.5Ho are the highest,reaching 1.28×10^(-10)mol·s^(-1)·cm^(-2)/39.8%,which is higher than the1.12×10^(-10)mol·s^(-1)·cm^(-2)/32.2%of Co_(0.2)Ni_(0.8)-MOF-74,and is about 14.3%/23.7%higher than that without doping,respectively.And the stability of Co_(0.2)Ni_(0.8)-MOF-0.5 Ho is good(after 80 hours of continuous testing,the current density did not significantly decrease).This is mainly due to doping,which gives Co_(0.2)Ni_(0.8)-MOF-74 a larger specific surface area and catalytic active sites.The catalyst doped at the same time has more metal cation centers,which increases the electron density of the metal centers and enhances the corresponding eNRR performance.
文摘Rare earth elements are indispensable raw materials for advanced aero-engines, special optical materials, and high-performance electronic products. With the development of the social economy, the global demand for rare earth resources is increasing, and rare earths have become a key metal for the development of new industries and frontier technologies that are highly valued both at home and abroad. Ion-adsorbed rare earth ores are an important source of rare earths, so the efficient green leaching of ion-adsorbed rare earths is important. Researchers found that the selection of an efficient green leaching agent for ion-adsorbed rare earths is based on the zeta potential of tailing clay minerals in addition to leaching efficiency, and both zeta potential and leaching ion concentration are related to mineral acidity and alkalinity, and the pH of tailing water suspension is a direct indicator of environmental water quality requirements. Therefore, the efficiency of the leaching process is closely integrated with the environmental evaluation, and the characteristics and correlation of the changes in zeta potential, pH, conductivity and pollutant concentration of the pulp of clay mineral content during the leaching process of ore leaching and tailings aqueous electrolyte solution leaching are studied by evaluating the leaching system, and a set of correlation leaching efficiency and environmental impact evaluation method is established based on the results of the above analysis, which is of scientific development of ion adsorption rare earth resources. It has important theoretical significance and practical application value.
基金V.ACKNOWLEDGEMENTSThisworkwassupportedbytheNationalNatu-ralScienceFoundationofChina(No.21334001andNo.91127030).V. ACKNOWLEDGEMENTS This work was supported by the National Natu- ral Science Foundation of China (No.21334001 and No.91127030).
文摘We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3+ or Sin^3+ into layer-structured 10,12-pentacosadiynoic acid (PCDA) nanopar- ticles to obtain PCDA/rare earth ions nanocomposites (PCDA-RE) and subsequently annealing PCDA-RE at the temperature slightly higher than the melting point of pure PCDA crystals, followed by topochemically polymerizing the annealed PCDA-RE. The polymerized PCDA-RE, i.e. poly(10,12-pentacosadiynoic acid)/rare earth ions nanocomposites (PDARE: PDA-Dy or PDA-Sm), are largely reversible (PDA-Sm) or even completely reversible (PDA-Dy) in the thermochromism, while, without the doping, pure PDA is completely irreversible. It is confirmed that, PDA-RE are also layer-structured with a d-spacing of 5.4 nm, higher than the d-spacing of pure PDA (4.7 nm). In PDA-RE, the rare earth ions form a layer in-between and interact strongly with the PDA bilayers, being responsible for the high degree or even the complete reversibility. This is the first example to make PDA completely reversible through the doping of rare earth ions; the annealing process is essential for the complete reversibility since it removes any defects in the structure.
基金Project supported by the National Natural Science Foundation of China (50571003)
文摘TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange (MO) in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4+ present the best activity to MO.
基金supported by the National Basic Research Program of China (973) (2007CB31407)Foundation for Innovative Research Groups of the NSFC (60721001)+1 种基金the Young Fund of Sichuan Province (08ZQ026-013)the National Natural Science Foundation of China (50972023, 50872078)
文摘Ca1-xRxCu3Ti4O12(R=La,Y,Gd;x=0,0.1,0.2,0.3) electronic ceramics were fabricated by conventional solid-state reaction method.The microstructure and dielectric properties as well as impedance behavior were carefully investigated.XRD results showed that the secondary phases with the general formula R2Ti2O7 existed at grain boundaries of rare earth doped ceramics,which inhibited abnormal grain growth.The dielectric constant decreased from 4×105 in pure CaCu3Ti4O12(CCTO) ceramics to 2×103 with rare earth doping....
文摘Materials with function of producing negative ions effection,containing valency-variable rare earth elements and semiconductor oxide,were fabricated.Free radicals produced by the materials were tested.The result shows that the materials can produce quite a few free radicals as·O^-_2 no matter whether they are under illumination of ultraviolet radiation or under visible light radiation,or under no light radiation, demonstrating semiconductor oxide can be catalysed under the visible light radiation.At the same time the result shows there is direct relation between the number of free radicals and of the negative ion produced by the materials,which meant that during photo-catalyzed and redox process of valency-variable rare earth elements free radicals translate into negative ions. A circular model is presented involving circulating change of valency-variable rare earth elements and water and oxygen absorbed on the surface of materials under the condition of photocatalysis.
基金supported by the start-up and OVPR seed Grant from Temple University
文摘Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been developed to analyze the concentration of rare earth ions using a smartphone camera. The success of this protocol relies on mesoporous silica nanoparticles(MSNs) with large-area negatively charged surfaces, on which the rare earth cations(e.g., Eu^(3+)) are efficiently adsorbed through electrostatic attraction to enable a ‘‘concentrating effect''. The initial adsorption rate is as fast as 4025 mg(g min)^(-1), and the adsorption capacity of Eu^(3+)ions in the MSNs is as high as 4730 mg g^(-1)(equivalent to ~41.2 M) at 70 °C. The concentrated Eu^(3+)ions in the MSNs can form a complex with a light sensitizer of 1,10-phenanthroline to significantly enhance the characteristic red emission of Eu^(3+)ions due to an ‘‘antenna effect'' that relies on the efficient energy transfer from the light sensitizer to the Eu^(3+)ions.The positive synergy of ‘‘concentrating effect'' and ‘‘antenna effect'' in the MSNs enables the analysis of rare earth ions in a wide dynamic range and with a detection limit down to ~80 nM even using a smartphone camera. Our results highlight the promise of the protocol in fieldwork for exploring valuable rare earth resources.
基金the University Grant Commission New Delhi for financial assistance through the Minor Research Project (No. 47-016/06)
文摘Nano-sized powders of rare-earth ions added CdFe2O4 ferrites were synthesized by oxalate co-precipitation method.The influence of R ions(R = Sm3+, Y3+, and La3+) on the microstructure and magnetic properties of CdFe2O4 ferrites was studied.XRD, SEM, FTIR, and magnetic hysteresis loops were used for analyzing the samples.The addition of R ions alters the structure of the powders and decreases the crystalline size, lattice constant, and grain size.The magnetic properties such as saturation magnetization, remanent magnetization, and magnetic moment increased due to addition of rare-earth ions in CdFe2O4 ferrite.The formation of secondary phase on the grain boundaries supports the abnormal growth.FTIR spectra show two absorption bands.Results suggest that the magnetic properties depend on the particular method of preparation and additives.
基金This work was partly supported by National Natural Science Foundation of China(Grant No.40325009)by“One-hundred Talent Program”of the Chinese Academy of Sciences.
文摘Coupled with a petrographical study, I carried out an ion probe study of rare earth element microdistributions in mineral phases of silicate inclusions from the Colomera ⅡE iron meteorite. Most mineral grains have homogeneous REEs, but show considerable inter-grain variations by a factor of 2 to 100. The whole rock REE abundances for Colomera, estimated by combining REE data with modal abundances, are relatively LREE-enriched with REEs of -10'CI, which suggest that Colomera silicates were highly differentiated and might represent a low degree partial melt (-10%) of a chondritic source. REE geochemistry of Colomera silicate inclusions points to an origin that involves differentiation, dynamic mixing, remelting, reduction, recrystallization, and subsequent rapid cooling near the surface of a planetary body.
基金This work was supported by the Zhejiang Provincial Natural Science Foundation and the Chinese University Doctoral Fund
文摘Pervaporation separation of water-acetic acid mixtures through Poly(AN-co-AA) membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigated for the first time. The results showed that the treatment with rare earth metal ions could greatly improve the characteristics of the separation of water-acetic acid mixtures.
文摘Well-ordered metal structures, i.e. arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used. These arrays were prepared by the metal evaporation on track membranes. Calculations of reso- nanee frequencies of tips regarded as semispheroids were done taking into account the interaction between dipoles of tips. They were used to discuss experimental results for media with Eu(NO3)3·6H2O salt basing on data for bulk silver dielectric function.
基金the National Natural Science Foundation of China (Nos. 50590405)the Natural Science Foundation of Fujian Province (No. A0610031)
文摘The limitation of the random walk theory of energy transfer between rare earth ions in crystals published in literatures is pointed out in this paper. A modified model, which can be used in any level of rare earth ion concentration when the interaction between donor and acceptor is different from that between donors, is introduced. measured fluorescence lifetimes of Yb^3+:YAl3(BO3)4 This model has been applied to analyze the with a series of Yb^3+ concentrations.
基金Project supported by the National Natural Science Foundation of China (Grant No 10674019)
文摘The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er(0.5)Yb(9.5):FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.
文摘In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.
基金Project supported by the National Natural Science Foundation of China(Grant No.11474096)the Science and Technology Commission of Shanghai Municipality,China(Grant Nos.14JC1401500,17ZR146900,and 16520721200)the Higher Education Key Program of He'nan Province of China(Grant No.17A140025)
文摘Improving the up-conversion luminescence efficiency crucial in several related application areas. In this work, of rare-earth ions via the multi-photon absorption process is we theoretically propose a feasible scheme to enhance the resonance-mediated two-photon absorption in Er3+ ions by shaping the femtosecond laser field with a rectangle phase modulation. Our theoretical results show that the resonance-mediated two-photon absorption can be decomposed into the on-resonant and near-resonant parts, and the on-resonant part mainly comes from the contribution of laser central frequency components, while the near-resonant part mainly results from the excitation of low and high laser frequency components. So, the rectangle phase modulation can induce a constructive interference between the two parts by properly designing the modulation depth and width, and finally realizes the resonance-mediated two-photon absorption enhancement. More- over, our results also show that the enhancement efficiency of resonance-mediated two-photon absorption depends on the laser pulse width (or laser spectral bandwidth), final state transition frequency, and intermediate and final state absorption bandwidths. The enhancement efficiency modulation can be attributed to the relative weight manipulation of on-resonant and near-resonant two-photon absorption in the whole excitation process. This study presents a clear physical insight for the quantum control of resonance-mediated two-photon absorption in the rare-earth ions, and there will be an important significance for improving the up-conversion luminescence efficiency of rare-earth ions.
基金This work was financially supported by the Hi-Tech Research and Development Program (863 Program) of China (No. 2002AA302304)the National Natural Science Foundation of China (No. 60121101)the Education Department Foundation of Jiangsu Province (JHOl-
文摘TiO_2 sols modified by rare earth (RE) ions (Ce^(4+), Eu^(3+), or Nd^(3+))were prepared by coprecipitation-peptization method. The photocatalysis activity was studied byinvestigating the photodegradation effects of active brilliant red dye X-3B. It is found that TiO_2sols modified by Ce^(4+), Eu^(3+), or Nd^(3+) have the anatase crystalline structure, which areprepared at 70℃. All RE^(n+)-TiO_2 sol samples have uniform nanoparticles with similar morphology,which are homogenously distributed in aqueous colloidal systems. The particle sizes are 10, 8, and12 nm for Nd^(3+)-TiO_2, Eu^(3+)-TiO_2, and Ce^(4+)-TiO_2, respectively. The character of ultrafineand positive charge sol particles contributes to the good adsorption of X-3B dye molecule on thesurface of titania (about 30% X-3B adsorption amount). Experimental results exhibit thatRE^(n+)-TiO_2 sol photocatalysts have the capability to photodegrade X-3B under visible lightirradiation. Nd^(3+)-TiO_2 and Eu^(3+)-TiO_2 show higher photocatalytic activity than Ce^(4+)-TiO_2,which is due to the difference of standard redox potential of RE^(n+)/RE^((n-1)+). RE^(n+)-TiO_2sols demonstrate more excellent interfacial adsorption and photodegradation effects to X-3B thanP_(25) TiO_2 crystallites. Moreover, the degradation mechanism of X-3B is proposed as dyephotosensitization and electron scavenging by rare earth ions.
文摘TiN coatings were deposited on polished substrates of W18Cr4V high speed steel by means of vacuum arc ion plating. The effect of cerium on adhesion between TiN coating and substrate was studied. The microstructures and composition of TiN coatings were also investigated by means of scanning electron microscope (SEM), Auger electron spectroscopy (AES), and X ray diffraction (XRD) technique. It was found that cerium is an effective modifying agent and the addition of suitable amount of cerium to TiN coatings can produce relatively excellent properties such as micro hardness, wear resistance, oxidation resistance and porosity. The experimental results show that the added cerium in TiN coatings makes a contribution to form the preferred direction along with a (111) or (222) close packed face, which may be one of the reasons that improves some properties mentioned above.
基金Project supported bythe Japan Societyfor the Promotion of Science (JSPS)
文摘Ce (Ⅳ) nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine (PVP) and quatemized PVP incorporated into porous silica matrix. The effect of nitric acid concentration (0.5~6 mol·L^-1) and temperature (278 ~318 K) on Ce( Ⅳ ) sorption efficiency was investigated. Sorption increased with increasing nitric acid concentration, indicating that [Ce(NO3)6]^2- complex is the main adsorbed Ce(Ⅳ) species. Oxidation of sorbents by adsorbed Ce ( Ⅳ ) species resulting in Ce ( Ⅲ ) release to the solution was observed. Pyridine based anion exchangers exhibited higher oxidation stability compared to the commercial strong base anion exchanger. Ce( Ⅳ ) reduction was temperature dependent and obeyed pseudo-first-order reaction kinetics. Column separation of Ce ( Ⅳ ) from La ( Ⅲ ) and Y ( Ⅲ ) was carried out from 6 mol·L^-1 nitric acid with PVP based anion exchanger. Reasonable Ce (Ⅳ) breakthrough capacity (0.7 mol·kg^-1 PVP) was achieved. No remarkable decrease of capacity was observed within 3 consequent runs. In contrast, Ce (Ⅲ) leakage due to reduction decreased and breakthrough capacity slightly increased. This effect was more pronounced with increasing temperature. Regeneration with 0.1 mol·L^- 1 nitric acid was successful (recovery 100% ± 4% ) and Ce solution of high purity ( 〉 99.97% ) with respect to La and Y content was gained.
文摘Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).
基金Projects(51664015,41602311,51774156) supported by the National Natural Science Foundation of China
文摘The ion exchange model of the leaching process was determined via batch leaching experiments using the Kerr model, with the selectivity coefficient experimentally determined to be 12.59×10^-10 L^2/g^2. Solute transport laws of ammonium ions (NH4 +) and rare earth ions (RE^3+) in column leaching were described by the convection-dispersion equation (CDE). The source and sink in the CDE were determined by the Kerr model. The CDE with strong nonlinearity was solved using the sequential non-iterative method. Compared with the breakthrough curve of RE^3+, the correlation coefficient between the simulated and experimental curves reached 0.8724. Therefore, this method can simulate the one-dimensional column leaching of weathered crust elution-deposited rare earth ore. Moreover, the effects of different concentrations of ammonium sulfate ((NH4)2SO4) solution on the leaching rate of rare earth were analyzed. The optimal concentration of the (NH4)2SO4 solution had a linear relationship with the rare earth grade.