LaSr_2Mn_2O_7 Ruddlesden-Popper manganites for oxygen reduction and electrochemical capacitors

LaSr_2 Mn_2 O_7,a Ruddlesden-Popper type bilayered perovskite,was investigated as oxygen catalyst for oxygen reduction reaction(ORR) and active electrode material for electrochemical capacitors in KOH solutions.XPS results show that Mn takes a mixed Mn~(2+),Mn~(3+)and Mn~(4+)valence state with an average valence of 3.4.As catalyst towards ORR,LaSr_2 Mn_2 O_7 and LaSr_2 Mn_2 O_7/acetylene black composite favor four electron pathways for ORR.LaSr_2 Mn_2 O_7/C composite shows a comparable onset potential for ORR to that of Pt/C electrode.The improved ORR activity of LaSr_2 Mn_2 O_7/acetylene black composite is attributed to the synergy between catalytic LaSr_2 Mn_2 O_7 and conductive acetylene black.As electrode material for electrochemical capacitors,LaSr_2 Mn_2 O_7 exhibits a maximum specific capacitance of 167.2 F/g with 62%faradic contribution at a scan rate of 1 mV/s in cyclic voltammetry test.     

Sub-10 nm lanthanide-doped SrFCl nanoprobes:Controlled synthesis,optical properties and bioimaging

Alkaline-earth dihalide nanocrystals(NCs) such as SrFCl, owing to their high chemical stability and low phonon energy, are excellent host materials for lanthanide(Ln~(3+)) doping to achieve desirable optical properties for various bioapplications, Herein, we report a novel strategy for the synthesis of sub-10 nm Ln~(3+)-doped SrFCl NCs with efficient upconverting and downshifting luminescence through a facile onestep hot-injection method. Utilizing the temperature-dependent upconverting luminescence(UCL) from the thermally coupled ~2H_(11/2) and ~4S_(3/2) levels of Er~(3+), we showed the potential of SrFCl:Yb,Er NCs as sensitive UCL nanoprobes for non-contact thermal sensing with a maximum detection sensitivity of 0.0066 K~(-1), which is among the highest values for thermal sensing based on Er~(3+)-activated UCL nanoprobes. Furthermore, by employing the intense downshifting luminescence from Tb~(3+) and Eu~(3+), we demonstrated the successful use of biotinylated SrFCl:Ce,Tb and SrFCl:Eu~(3+) nanoprobes for biotin receptor-targeted cancer cell imaging, thus revealing the great promise of SrFCl:Ln~(3+) nanoprobes for versatile bioapplications.     

Structure and electrochemical hydrogen storage behaviors of Mg-Ce-Ni-Al-based alloys prepared by mechanical milling

The influences of milling time and Ce content on the electrochemical property and micro structure of asmilled Mg_(1-x)Ce_xNi_(0.9)Al_(0.1)(x=0,0.02,0.04,0.06,0.08)+50 wt%Ni alloys were investigated systematically.The as-milled alloys have an outstanding activation property.The cycle stability conspicuously grows up with milling time and Ce proportion increasing.The capacity retention rate at 100 th cycle of x=0.02 alloy augments from 47% to 63% when prolonging milling time from 5 to 30 h and it grows from55% to 82% for the 30 h milled alloy with Ce content growing from 0 to 0.08.The discharge capacity of x=0.02 alloy grows up invariably with milling time prolonging,while that of the 30 h milled alloys has the maximal value of 578.4 mAh/g with Ce content increasing.Moreover,the electrochemical kinetic properties of alloys significantly improve with milling duration extending,while they have the maximal values with Ce proportion varying.     

CeO2-clay composites for ultra-long cycle life electrochemical capacitive energy storage application

The lattice expansion caused by the reduction of Ce(Ⅳ) to Ce(Ⅲ) impeded the development of the CeO₂as an effective electrode material for electrochemical supercapacitors.Herein,we prepared CeO₂-clay composites through a one-step hydrothermal method.The interlayer structures of clays efficiently accommodate volume changes induced by crystal lattice expansion to achieve ultra-long cycle stability.After 60000 charge-discharge cycles,the capacitance retention rate of the assemb...     

Characterization and electrochemical performance of CeO2 and Eu-doped CeO2 films as a manganese redox flow battery component

Hexagonal CeO_2 and Eu-doped CeO_2 nanoparticles were obtained using a facile microwave-hydro thermal method under mild conditions and their application towards manganese redox flow battery component were studied. The structural properties were studied by X-ray diffraction and indicate that samples present a fluorite structure. Raman spectroscopy shows Eu3+ ions substitute Ce~(4+) and generate oxygen vacancies. Electrochemical properties of pure and Eu-doped CeO_2 films deposited at graphite substrates investigated by cyclic voltammetry and galvanostatic charge—discharge indicate that dopant concentration affects the electrochemical properties of CeO_2. The increase in the reversibility redox of electrochemical systems observed is attributed to coexistence of Ce~(4+)/Ce~(3+) redox couple confirmed by XPS.Charge—discharge tests display coulombic and voltage efficiency values of above 80% and 90%, respectively. The obtained specific capacity for Ce_(0.99)Eu_(0.01)O_2(372.49 mAh/g) and pure oxide(334.84 mAh/g)indicates that both samples are promising for application in Mn-batteries.     

Near-infrared luminescent Nd~(3+)/Yb~(3+)-codoped metal-organic framework for ratiometric temperature sensing in physiological range

Self-calibrating luminescent thermometry employing luminescence within the optical transparency windows provides a promising prospect for temperature measurement in the biological fields.In this work,a new Nd~(3+)/Yb~(3+)-codoped metal-organic framework Nd_(0.95)Yb_(0.05)BPTC showing threedimensional anionic network,obtained by reacting ligand [1,1'-biphenyl]-3,3',5,5'-tetracarboxylic acid(H_4BPTC) with Nd~(3+) and Yb~(3+) ions under solvothermal conditions,is reported.Upon 808 nm photoexcitation,Nd_(0.95)Yb_(0.05)BPTC simultaneously emits the characteristic near-infrared luminescence of Nd~(3+) and Yb~(3+) ions based on the efficient energy transfer from Nd~(3+) to Yb~(3+) ions.In addition,the emission intensity ratio of Yb~(3+) and Nd~(3+) shows good exponential-like response to temperature in the physiological range of 293-323 K.The feature properties of Nd_(0.95)Yb_(0.05)BPTC include near-infrared absorption and emission,favorable temperature sensitivity and accurate temperature uncertainty,as well as good chemical stability,making such system useful in biomedical applications.     

Using europium(III) complex of 1,4,7,10-tetraazacyclododecane-1,4,7-triacedic acid Eu.DO3A as a luminescent sensor for bicarbonate

Sensing of analytes in biological fluids and biotechnological production media remains a challenge. Here, the luminescent response of the europium (III) complex of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) to bicarbonate was investigated in detail. The response of Eu.DO3A to changes in bicarbonate concentration was studied in different buffers, and the influence of ionic strength, pH, and specific ions was determined. The response is found to depend on pH and ionic strength, but it is not possible to separate contributions from the sensing event from those in the bicarbonate activity. Prior to demonstrating the ability to determine the bicarbonate concentration in bioproduction media and serum, the influence of competing carboxy anions was evaluated. It is established that while competing anions bind stronger to the responsive complex, at the relevant concentration their contribution to the recorded signal is negligible. We are thus able to conclude that Eu.DO3A is a good platform for building a bicarbonate sensor.     

Single phase A_2B_7-type La-Mg-Ni alloy with improved electrochemical properties prepared by melt-spinning and annealing

La-Mg-Ni alloys were prepared by melt-spinning with different cooling rates and followed by annealing.Elevation of the cooling rate leads to refinement of the grains size and increasing of the abundance of LaNis.Annealing is favorable to formation of the A_2 B_7-type phase and promotes the discharge capacity,cycling stability and high rate discharge ability of the as-spun alloys.Phase constitution of the annealed alloys is found to be closely related to the microstructure of the as-spun alloys.A single phase A_2 B_7-type microstructure is obtained in the annealed alloy which is attributed to the lower abundance of the LaNis of the original alloy spun with lower cooling rate.Formation of the single phase A_2 B_7-type microstructure is also ascribed to the isolated and homogeneous distribution of the morphology of the as-spun alloy.The single phase alloy presents higher discharge capacity and better cycling stability compared with other annealed alloys.     

Magnetic and thermosensitive luminescent nanocomposites based on Fe3O4/SiO2/poly (N-isopropylacrylamide)/lanthanide-polyoxometalates and their controllable luminescence properties

Magnetic and temperature-responsive luminescent composites based on poly(N-isopropylacrylamide),magnetic nanoparticles and Na_9[EuW_(10)O_(36)] were fabricated. The composites were investigated by IR, UV,XRD, TGA, SEM and TEM. The prepared nanocomposites exhibit good superparamagnetic property and thermo-responsive switchable luminescence properties. The multifunctional nanocomposites can be separated by external magnetic field. Moreover, the nanocomposites exhibit an appreciable temperature response, and the red luminescence of the nanocomposites in solution can be controlled by the temperature stimuli. The hydrogel emits strong redluminescence in solution at 25 ℃,which can be seen by naked eyes. When the external temperature is 40 ℃, the red luminescence almost disappears in solution.It is expected that the multifunctional nanoparticles have potential applications in the field of biomedicine.     

Structure regulation for ultra-high luminescence quantum yield lanthanide complex and simultaneous detection of cancer marker and ferrous ion

The exploitation of a highly selective and sensitive probe to detect both cancer marker and metal ion is of great importance.In this work,the "one stone two bird" agent of 1,10-phenanthroline(phen) is designed to disrupt the polymeric lanthanide MOFs(LnMOFs,[Ln(CHO_2)_3]n,Ln=Tb,la;Eu,1 b,CHO2=formic acid) {[Ln(CHO_2)_4·(C_2 H_8 N)]_n,Ln=Y,2 a;Gd,2 b;Dy,2 c,C_2 H_8 N=dimethylamine}) into a soluble mononuclear species [Ln(phen)2(NO_3)_3,Ln=Tb,3 a;Eu,3 b] as well as to provide an antenna for efficient photons absorption,resulting in an ultra-high luminescence quantum yield(QY,90%) europium complex.The luminescence QY is among the highest record of monomeric(zero-dimensional) lanthanide complexes.Furthermore,mononuclear Tb3+complex(3 a) functions as a multiplex sensor towards both Fe2+and cancer marker of 5-hydroxyindole-3-acetic acid(5-HIAA).Importantly,the limit of detection(LOD)for sensing 5-HIAA is an ultra-sensitive value of 1 × 10 s mol/L,which is even lower than that necessary for the early diagnosis of carcinoid tumors.More interestingly,sensing results in simulated urine reveals that 3 a has potential application for early diagnosis in the clinic.     

Effect of reduced graphene oxide-supported copper addition on electrochemical properties of La0.7Mg0.3Ni2.8Co0.5 electrodes

The reduced graphene oxide-supported copper(Cu@rGO) nanocomposite was introduced to improve the electrochemical properties of La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5)alloy electrodes.Experimental results show that adding Cu@rGO nanocomposite with mass fractions of x wt%(x=0,3,6 and 9) to the alloy electrodes provides electrodes with maximum discharge capacities of 368.9 mAh/g(x=0),373.2 mAh/g(x=3),407.3 mAh/g(x=6) and 398.6 mAh/g(x=9),and high-rate dischargeabilities at a discharge current density of1200 mA/g of 40.5%(x=0),64.0%(x=3),82.0%(x=6) and 76.0%(x=9).The addition of Cu@rGO nanocomposite also provides alloy electrodes with hydrogen diffusion coefficients of 3.7×10~(-10) cm~2/s(x=0),4.1×10~(-10) cm~2/s(x=3),4.2×10~(-10) cm~2/s(x=6) and 4.0×10~(-10) cm~2/s(x=9).Clearly,the addition of 6 wt%Cu@rGO nanocomposite not only increases the electrochemical capacity of La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5) alloy electrodes,but also improves their electrochemical kinetic properties.     

Trace detection of Ce3+ by adsorption strip voltammetry at a carbon paste electrode modified with ion imprinted polymers

To develop a convenient method for sensitive and selective determination of Ce3+ in aqueous phase with complicated matrices, a carbon paste electrode(CPE) modified with ion imprinted polymers(IIPs) were fabricated. The polymers were prepared by precipitation polymerization using Ce3+ as template, allyl phenoxyacetate(APA) as monomer, ethylene glycol dimethacrylate(EGDMA) as crosslinker and azobisisobutyronitrile(AIBN) as initiator under the molar ratio of Ce3+, APA and EGDMA as 1:4:40, respectively. Ce~(3+) was detected directly by differential pulse adsorptive stripping voltammetry(DPASV) and its oxidation peak appears at about 0.93 V. All parameters affecting the sensor's response are optimized and a calibration curve is plotted at a linear range of 1.0 × 10~(-6)-1.0 x 10~(-5) mol/L and 1.0×10~(-5)-2.0 × 10~(-4)mol/L with the detection limit of 1.5 × 10~(-7) mol/L. All other rare earth ions have no interference with the determination of Ce~(3+) even at a concentration 500 times higher than that of Ce~(3+).This sensor was successfully applied to determination of Ce~(3+) in two catalyst sample solutions with RSD≤3.3%(n = 5)and recoveries in the range of 99.2%-106.5% at our optimal conditions.     

Recent development in upconversion nanoparticles and their application in optogenetics: A review

Ion channels present in the plasma membrane are responsible for integration and propagation of electric signals, which transmit information in nerve cells. Malfunction of these ion channels leads to many neurological diseases. Recently, optogenetic technology has gained a lot of attention for the manipulation of neuronal circuits. Optogenetics is a neuromodulation approach that has been developed to control neuronal functions and activities using light. The lanthanide-doped upconversion nanoparticles (UCNPs) absorb low energy photons in near-infrared (NIR) window and emit high energy photons in the visible spectrum region via nonlinear processes. In the last few decades, UCNPs have gained great attention in various bio-medical applications such as bio-imaging, drug delivery and optogenetics. The near-infrared illumination is considered more suitable for optogenetics application, due to its lower degree of light attenuation and higher tissue penetration compared to visible light. Therefore, UCNPs have been considered as the new promising candidates for optogenetics applications. Upconversion nanoparticle-mediated optogenetic systems provide a great opportunity to manipulate the ion channel in deep tissue. Herein, we summarize the upconversion photoluminescence in lanthanide doped nanomaterials and its mechanisms and several approaches adopted to tune emission color or enhance upconversion efficiency. Recent advances of lanthanide-doped UCNPs design strategy and their mechanism are reviewed. Then, we discuss the neural circuitry modulation using upconversion nanoparticles mediated optogenetics. Moreover, the future perspectives towards optogenetics are also included.     

Reaction between tetravalent cerium ion and chloride ion and effect of thiourea using cyclic voltammetry

To monitor the reaction between Ce⁴⁺ ion and Cl^– ion at the electron level, an electrochemical experiment was designed in this work. Herein, the intermediate and final products that may be produced during the redox reaction are directly tracked by using cyclic voltammetry, and the influences of Ce⁴⁺ ion concentration, temperature and F^– ion on the reduction peak potential of Ce⁴⁺ ion were investigated. The results show that Ce⁴⁺ ion reacts with Cl^– ion through an irreversible reaction without any intermediate products, and the rate-determining step of the reaction is diffusion during the electrode reaction. The effects of temperature (20–40 °C) and Ce⁴⁺ ion concentration (0.04–0.12 mol/L) on the reduction peak potential of Ce⁴⁺ ion can be ignored, but the higher the molar ratio of F^– to Ce⁴⁺ (0–3 mol/mol), the more easily the reduction of Ce⁴⁺ ion to Ce³⁺ ion occurs. Additionally, the Ce⁴⁺ ions are preferentially reduced by thiourea when thiourea is added in the HCl solution, and thiourea inhibits the oxidation of Cl^– ions to Cl₂ by forming a complex with Cl^– ions. This work provides a theoretical basis for the role of thiourea in inhibiting Cl₂ production and offers a new way to find new reductants.     

Hierarchical porous cellulose/lanthanide hybrid materials as luminescent sensor

Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions (Eu³⁺, Tb³⁺) were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulose framework through coordination with the carboxylic groups of the cellulose. Hybrid materials were fabricated as hydrogel and aerogel. As shown by SEM and pore parameters, aerogel materials which were obtained by supercritical CO₂ drying show hierarchical porous structure. The photoluminescence spectrum of the hybrid materials shows the characteristic red emission of Eu³⁺ ion and green emission of Tb³⁺. Further luminescent investigations reveal that these hybrid materials can detect Fe³⁺ with relative selectivity and high sensitivity, which suggests that the hybrid materials could be a promising luminescent probe for selectively sensing Fe³⁺ ion.     

Recent progress in synthesis of lanthanide-based persistent luminescence nanoparticles

Persistent luminescence nanoparticles(PLNPs) are a kind of phosphors that can remain luminescent for seconds to several days after the stoppage of excitation.Lanthanides show the special capability to largely broaden the emission range and enhance the luminescence intensity of PLNPs due to their dense energy structure and unique electronic configurations.In the past decades,various methods have been developed for the synthesis of lanthanide-based PLNPs with excellent pe rsistent luminescence pro...     

Sorption of lanthanide ions on biochar composites

Sorption of lanthanum(Ⅲ), cerium(Ⅲ) and neodymium(Ⅲ) ions from the aqueous solutions of mixtures through adsorption on the biochar composites was investigated as a function of sorbent mass, pH, phase contact time and initial concentration of solutions at 295 K. The maximum removal of lanthanide ions takes place under the following conditions: 0.1 g of sorbent mass, pH 4 and 360 min contact time for all studied initial concentrations of solutions. Kinetics of La(Ⅲ), Ce(Ⅲ) and Nd(Ⅲ) ions sorption proceeded by a fast initial uptake reached equilibrium. This process was modelled by means of the pseudo first order, pseudo second order, intraparticle diffusion and Elovich models. The desorption of three lanthanide ions by nitric, hydrochloric and sulfuric acids at a concentration of 1 mol/L from biochar composites was also studied. In order to investigate the sorption mechanism FTIR, XRD and XPS analyses were performed after sorption of ions from the mixture.     

Voltammetric determination of venlafaxine as an antidepressant drug employing Gd2O3 nanoparticles graphite screen printed electrode

Graphite screen printed electrode modified with Gd_2 O_3 nanoparticles(Gd_2 O_3/SPE) was developed for the determination of venlafaxine(VF). The Gd_2 O_3 nanoparticles were thoroughly characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD) analyses. To study the electrochemical behaviour of venlafaxine cyclic voltammetry(CV), chronoamperometry(CHA)and differential pulse voltammetry(DPV) were employed. These studies reveal that the oxidation of venlafaxine is facilitated at Gd_2 O_3/SPE. After optimization of analytical conditions, analysis of venlafaxine using the modified electrode in 0.1 mol/L PBS(pH 7.0) demonstrates that the peak currents corresponding to venlafaxine vary linearly with its concentration in the range of 5.0 ×10~(-6)-9.0 × 10~(-4) mol/L. The detection limit(S/N = 3) of 2.1 × 10~(-7) mol/L is obtained for venlafaxine using DPV. The prepared modified electrode benefits from advantages such as simple preparation method, high sensitivity and low detection limit.Moreover, the evaluation of practical applicability of this proposed method is successful in the identification of venlafaxine in pharmaceutical formulations, urine and water samples.     

Removal of organic pollutants by lanthanide-doped MIL-53(Fe) metal-organic frameworks:Effect of dopant type in magnetite precursor

A series of undoped and lanthanide doped MIL-53(Fe)/Ln-Fe₃O₄(Ln=La,Nd,or Gd) metal-organic frameworks(MOFs) were prepared by the solvothermal method.All prepared samples were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),Brunauer-Emmett-Teller(BET) measurements,scanning electron microscopy(SEM),and thermal analysis.XRD and FT-IR results ascertain the successful MOF formation for all prepared samples.MIL-53(Fe)/La-Fe₃O_...     

Alternating copolymerization of CO2 and cyclohexene oxide initiated by rare-earth metal complexes stabilized by o-phenylenediamine-bridged tris(phenolate) ligand

A series of o-phenylenediamine bridged tris(phenolate) ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^tBu),and yttrium(complex 3) complexes stabilized by ligand of buiky tert-butyl substituents are mononuclear,whereas neodymium complexes 2^Me and 2^C1 bearing smaller methyl and chloro substituents are dinuclear,respectively.They were applied in the alternating copolymerization of CO₂