Nanocomposites of Polydiacetylene and Rare Earth Ions with Reversible Thermochromism

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.

Synthesis and Photocatalytic Activity of TiO_2/V_2O_5 Composite Catalyst Doped with Rare Earth Ions

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.

Rare earth doped CaCu_3Ti_4O_(12) electronic ceramics for high frequency applications

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....

Mesoporous SiO_2 Nanoparticles:A Unique Platform Enabling Sensitive Detection of Rare Earth Ions with Smartphone Camera

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.

PERVAPORATION SEPARATION OF WATER-ACETIC ACID MIXTURES THROUGH AN-co-AA MEMBRANES TREATED WITH RARE EARTH METAL IONS

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.

Luminescence enhancement of rare earth ions by metal nanostructures

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.

A Theoretical Model of Energy Transfer between Rare Earth Ions in Crystals

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.

Improved anti-Stokes energy transfer between rare earth ions in Er(0.5)Yb(9.5):FOV oxyfluoride vitroceramics explains the strong color reversal

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.

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

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.

The Electrocatalytic Performance of Rare Earth Ion Doped Co_(0.2)Ni_(0.8)-MOF-74 Catalyst for Nitrogen Reduction

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.

Rare earth ion modified TiO_2 sols for photocatalysis application under visible light excitation

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.

Rare earth oxides in zirconium dioxide:How to turn a wide band gap metal oxide into a visible light active photocatalyst

In the present study, we investigated the effect of cerium and erbium doping of the zirconium dioxide matrix. We synthesized doped samples using hydrothermal process. The amounts of dopant used were 0.5%, 1% and 5% molar(rare earth oxide over zirconium dioxide) respectively. The samples have been studied via X-ray Diffraction measurements for the structural characterization. UV visible diffuse reflectance was used for the optical analysis, Brunauer-Emmett-Teller(BET) model for the measurement of the surface area. Finally the samples have been analysed via electron paramagnetic resonance(EPR) for the electronic characterization. Then we tested the new synthetized materials to determine their photocatalytic activity in the reaction of degradation of methylene blue performed under irradiation by diodes(LEDs) emitting exclusively visible light.

Synthesis and Crystal Structure of a Novel 1D Chain-like Organic Inorganic Hybrid Rare Earth Derivative of Polyoxometalate: H_(0.5)[Sm(H_2O)_6]_(0.25)[Sm(H_2O)_5]_(0.25){[Sm(H_2O)_7][Sm(H_2O)_2-(DMSO)][SiW_(11)O_(39)]}·4.5H_2O

A 1D chain-like organic-inorganic hybrid rare earth derivative of polyoxometalate H0.5[Sm（H2O）6]0.25[Sm（H2O）5]0.25{[Sm（H2O）7][Sm（H2O）2（DMSO）][SiW11O39]}·4.5H2O has been firstly synthesized by reaction of α-K8SiW11O39.13H2O, HClO4, Sm2O3 with dimethyl sulfoxide （DMSO） and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. The neighboring polyanionic units {[Sm（H2O）7][Sm（H2O）2（DMSO）][SiWHO39]}^2- are bridged together to a 1D chain structure by means of [Sm（H2O）2（DMSO）]^3＋ ion.

Rare Earth Ion Yb^3+ Doping of Bi2WO6 with Excellent Visible-light Photocatalytic Activity

The rare earth ion Yb^3+ doped Bi2WO6 photocatalysts were synthesized by hydrothermal method.Moreover,XRD,XPS,FESEM,TEM,Ramam,N2 adsorption-desorption isotherm measurements and UV-vis diffusion reflectance spectra were used to characterize the Yb^3+ doped Bi2WO6 photocatalysts.The morphology,specific surface area,and pore volume distribution were greatly affected after Yb3+ ions doping.Photocatalytic performance of Bi2WO6 was effectively enhanced after Yb3+ ions doping,6% Yb^3+ doped Bi2WO6 had the best photocatalytic performance,and 96.2% Rhodamine B was degradated after irradiated 30 min,which was 1.29 times that of the pristine one.The enhanced photocatalytic performance was due to the increased specific surface area,decreased energy band gap and inhibition of photoelectron-hole recombination after Yb3+ ions doping.

Correlation Evaluation of Ion Adsorption-Based Rare Earth Leaching Performance Based on Zeta Potential Drop Leaching

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.

Influence of Nd^(3+) concentration on mid-infrared emission in PbF_(2) crystal co-doped with Ho^(3+) and Nd^(3+) ions

A promising series of Ho_(y)Nd_(x)Pb_((1-x-y))F_2(x = 0, 0.01, 0.02, 0.03, 0.04;y = 0.02) crystals was grown by the Bridgman method. The influence of the Nd^(3+)ions concentration on mid-infrared(~2.0, ~2.9 and ~3.9 μm)fluorescence emissions of Ho^(3+)ions in the PbF_(2) crystal excited by 808 nm laser diode was investigated in this work. The energy transfer mechanism between Nd^(3+)ions and Ho~(3+)ions under different concentrations of the Nd^(3+)ions was systematically analyzed. The results show that the Nd^(3+)ions have good sensitization and deactivation effect on the Ho^(3+)ions to stimulate the mid-infrared fluorescence emissions. The experimental analysis proves that the sensitization efficiency of the Nd^(3+)ions is relatively stable at around 93.45% with varying Nd^(3+)-doping concentrations. Concentration dependence studies indicate that the concentration of the Nd^(3+)ions has significant influence on mid-infrared emissions.When the doping concentration of the Nd^(3+)ions is up to 2.0 at%, the intensity of ~2.0, ~2.9 and ~3.9 μm emissions all reach the maximum. The output characteristics of a 3.9 μm laser are simulated, and it is found that with the increase of the Nd^(3+)-doping concentration, the peak power, pulse width, and peak energy all meet the trend of first increasing and then decreasing, and Ho_(0.02)Nd_(0.02)Pb_(0.96)F_(2) crystal displays the best performance. All the results show that the Nd^(3+)/Ho^(3+)co-doped PbF_(2) crystals might act as a useful optical medium for mid-infrared laser applications.

Enhancing leaching efficiency of ion adsorption rare earths by ameliorating mass transfer effect of rare earth ions by applying an electric field

Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.

Preparation and up-conversion luminescence properties of Er:YbAG and Er:YAG single crystals

High quality optical single crystals of cubic Yb_(2.96)Er_(0.04)Al_(5)O_(12)and Y_(2.96)Er_(0.04)A_(l5)O_(12)were successfully pre-pared using the OFZ method.The 980 nm photon absorption intensity by Yb_(2.96)Er_(0.04)Al_(5)O_(12)crystal is much larger than that in Y_(2.96)Er_(0.04)A_(l5)O_(12)crystal,the transmission of Yb_(2.96)Er_(0.04)Al_(5)O_(12)crystal is lower than that of Y_(2.96)Er_(0.04)A_(l5)O_(12)crystal,because the density of Yb_(2.96)Er_(0.04)Al_(5)O_(12)single crystal(6.604 g/cm^(3))is larger than that of Y_(2.96)Er_(0.04)A_(l5)O_(12)single crystal(4.529 g/cm^(3)).The up-conversion luminescence spec-tra of the crystals excited by 980 nm laser show several distinct groups of emission peaks at-544 and-556 nm,as well as-650 and-667 nm.The peak intensities of the up-conversion luminescence spec-trum for the Yb_(2.96)Er_(0.04)Al_(5)O_(12)crystal were much higher than those for the Y_(2.96)Er_(0.04)A_(l5)O_(12)crystal.Over-all,the results of the present study suggest that Yb_(2.96)Er_(0.04)Al_(5)O_(12)single crystal may have advantages over Y_(2.96)Er_(0.04)A_(l5)O_(12)single crystal for luminescence in solid-state lasers.

Multiferroic and in-plane magnetoelectric coupling properties of BiFeO_3 nano-films with substitution of rare earth ions La^(3+) and Nd^(3+)

Single-phase multiferroic BiFeO3 and Bi（0.9）（La/Nd）（0.1）FeO3（doped with rare earth ions La-（3＋） and Nd-（3＋）） films grown on（111）-Pt/Ti/SiO2/Si substrate were prepared via sol-gel method and a subsequent rapid thermal process. The phase composition, microstructure, ferroelectric, dielectric, ferromagnetic properties were investigated, and meanwhile, the in-plane magnetoelectric（ME） coupling effects of the films were reported and studied for the first time in this work. Structural characterization by X-ray diffraction and scanning electron microscopy showed that both BiFeO3 and Bi（0.9）（La/Nd）（0.1）FeO3 exhabited a rhombohedral structure with（111） preferred orientation. The results of the physical properties indicated that the introduction of rare earth ions improved significantly the polarization, magnetization and dielectric properties than the undoped BiFeO3 crystals, and it enhanced effectively the in-plane ME coupling（the ME coupling coefficient αE increased from 0.13 in the pure BiFeO3 to 0.21 in Bi（0.9）La（0.1）FeO3 and 0.34 V/（Oe·cm） in Bi（0.9）Nd（0.1）FeO3）. The mechanism of these phenomena was investigated systematically.

Photocatalytic activity of perovskite SrTiO_(3)catalysts doped with variable rare earth ions

In this work,15 types of rare earth(Re)ions,including Y^(3+),La^(3+),Ce^(3+),Pr^(3+),Nd^(3+),Sm^(3+),Eu^(3+),Gd^(3+),Tb^(3+),Dy^(3+),Ho^(3+),Er^(3+),Tm^(3+),Yb^(3+)and Lu^(3+)doped perovskite SrTiO_(3)powders were synthesized by solgel method.The influence of Re ions doping on the crystal structure,morphology and optical property as well as the photocatalytic activity for the photodegradation of rhodamine B(RhB)was investigated in detail when the synthesized Re ions doped SrTiO_(3)powders were served as catalysts.The presented results revealed that the crystal structure is invariable,whereas the morphology and the optical bandgap are variable for the resultant SrTiO_(3)powders when different Re ions were incorporated into the SrTiO_(3)lattice.The relatedness between the morphology,optical property and photocatalytic activity of the synthesized SrTiO_(3)catalysts doped with variable Re ions were analyzed deeply,providing an insight into the influence factors on the photocatalytic activity of catalysts.