Frenkel Defect-modulated Anti-thermal Quenching Luminescence in Lanthanide-doped Sc2 (WO4 )3.

Although large amount of effort has been invested in combating thermal quenching that severely degrades the performance of luminescent materials particularly at high temperatures, not much affirmative progress has been realized. Herein, we demonstrate that the Frenkel defect formed via controlled annealing of Sc2 (WO4 )3 :Ln (Ln=Yb, Er, Eu, Tb, Sm), can work as energy reservoir and back-transfer the stored excitation energy to Ln3+ upon heating. Therefore, except routine anti-thermal quenching, thermally enhanced 415-fold downshifting and 405-fold upconversion luminescence are even obtained in Sc2 (WO4 )3 :Yb/Er, which has set a record of both the Yb3+ -Er3+ energy transfer efficiency (>85 %) and the working temperature at 500 and 1073 K, respectively. Moreover, this design strategy is extendable to other hosts possessing Frenkel defect, and modulation of which directly determines whether enhanced or decreased luminescence can be obtained. This discovery has paved new avenues to reliable generation of high-temperature luminescence.

The Synergetic Effect Induced High Electrochemical Performance of CuO/Cu2O/Cu Nanocomposites as Lithium-Ion Battery Anodes.

Due to the high theoretical capability, copper-based oxides were widely investigated. A facile water bath method was used to synthesis CuO nanowires and CuO/Cu2O/Cu nanocomposites. Owing to the synergetic effect, the CuO/Cu2O/Cu nanocomposites exhibit superior electrochemical performance compared to the CuO nanowires. The initial discharge and charge capacities are 2,660.4 mAh/g and 2,107.8 mAh/g, and the reversible capacity is 1,265.7 mAh/g after 200 cycles at 200 mA/g. Moreover, the reversible capacity is 1,180 mAh/g at 800 mA/g and 1,750 mAh/g when back to 100 mA/g, indicating the excellent rate capability. The CuO/Cu2O/Cu nanocomposites also exhibit relatively high electric conductivity and lithium-ion diffusion coefficient, especially after cycling. For the energy storage mechanism, the capacitive controlled mechanism is predominance at the high scan rates, which is consistent with the excellent rate capability. The outstanding electrochemical performance of the CuO/Cu2O/Cu nanocomposites indicates the potential application of copper-based oxides nanomaterials in future lithium-ion batteries.

One-Pot Synthesis and High Electrochemical Performance of CuS/Cu1.8S Nanocomposites as Anodes for Lithium-Ion Batteries.

CuS and Cu1.8S have been investigated respectively as anodes of lithium-ion batteries because of their abundant resources, no environment pollution, good electrical conductivity, and a stable discharge voltage plateau. In this work, CuS/Cu1.8S nanocomposites were firstly prepared simultaneously by the one-pot synthesis method at a relatively higher reaction temperature 200 °C. The CuS/Cu1.8S nanocomposites anodes exhibited a high initial discharge capacity, an excellent reversible rate capability, and remarkable cycle stability at a high current density, which could be due to the nano-size of the CuS/Cu1.8S nanocomposites and the assistance of Cu1.8S. The high electrochemical performance of the CuS/Cu1.8S nanocomposites indicated that the CuxS nanomaterials will be a potential lithium-ion battery anode.

Modulation of lanthanide luminescence via an electric field.

The modulation of luminescence via external stimuli such as temperature, mechanical stress, hydrostatic pressure, as well as electric and/or magnetic fields, has witnessed great progress, enabled the disclosure of new principles and energy transfer pathways, and widened applications. However, investigations on the luminescence modulation of lanthanide ions doped in semiconductors via an applied electric field are still absent. Herein, for the first time, we have demonstrated the in situ, real-time, and reversible modulation of the luminescence of Eu3+ doped in SnO2 nanocrystals by manipulating the recombination rate of photo-generated electrons and holes, and the accompanied energy transfer mode in terms of linear and quasi-sinusoidal, from semiconductor to lanthanide ions. Following the same principle, the modulation of near infrared responsive Er3+ in SnO2 and the visible luminescence of perovskite nanocrystals is further realized. This study offers extra methodologies for luminescence modulation, in addition to those already reported for ferro- and/or piezoelectric-hosted luminescent materials.

A stable mixed lanthanide metal-organic framework for highly sensitive thermometry.

A family of lanthanide-based MOFs (Ln-MOFs) with high thermal and chemical stability have been successfully synthesized by a solvothermal method. Owing to the intrinsic robustness of the framework and temperature-dependent luminescence behaviour of lanthanides, Eu3+/Tb3+-mixed MOFs ([(CH3)2NH2]Eu0.036Tb0.964BPTC) have also been successfully synthesized and targeted for developing excellent luminescent thermometers. The obtained mixed Ln-MOF exhibits ratiometric temperature sensing based on the distinguished characteristic emission of lanthanides with a wide temperature range from 77 K to 377 K. Particularly, the temperature sensor shows good linear responses from 220 K to 310 K with the maximum relative sensitivities (Sm) of 9.42% per K at 310 K. This value is comparable to those of the most excellent Ln-MOF thermometers reported. Besides, the temperature-dependent luminescent colours could also be systematically tuned from green, through yellow to red with increasing temperature, which can be clearly and directly observed even by the naked eye or a camera, thus also allowing colorimetric luminescence thermometry.

Erbium(iii)-based metal-organic frameworks with tunable upconversion emissions.

A series of lanthanide-based metal-organic frameworks (Ln-MOFs) with significantly improved and tunable upconversion emissions were prepared. Y-MOFs co-doped with Yb3+/Er3+ ions have exhibited characteristic upconversion emissions at 520, 545, and 658 nm under 980 nm laser excitation, the intensities of which vary with Yb3+/Er3+ concentrations. In addition, experimental results have indicated that an excited state absorption mechanism is responsible for the upconversion process of Y-MOF:Yb/Er materials. This study has provided a novel design principle and experimental basis for the preparation of luminescent Ln-MOF materials.

Interconversion between KSc2F7:Yb/Er and K2NaScF6:Yb/Er nanocrystals: the role of chemistry.

Scandium (Sc) sits at a unique position in the periodic table, i.e., the junction of the top of the rare earth column and the beginning of the transition metal row. Studies have shown that Sc-based nanomaterials are very sensitive to the surrounding chemical environment. A simple adjustment of the chemical reaction conditions such as temperature, surfactant molecules, and solvents (e.g., oleic acid (OA) or 1-octadecene (OD)) can easily lead to different products in terms of chemical composition and phase structure. Herein, under purposely adjusted reaction conditions, we have investigated the interconversion process between two representative Sc-based nanomaterials, that is, nanocrystals of orthorhombic KSc2F7:Yb/Er and cubic K2NaScF6:Yb/Er, both of which have characteristic red upconversion luminescence and high similarity in chemical composition and phase structure. Experimental results have indicated that conversion from KSc2F7:Yb/Er to K2NaScF6:Yb/Er may start from the edge of the nanocrystal where K+ in KSc2F7:Yb/Er was gradually substituted by the post-introduced Na+ in the solution and finally KSc2F7:Yb/Er nanorods were broken and K2NaScF6:Yb/Er nanocubes were formed. On the other hand, a simple variation of the OA : OD ratio facilitates the dissolution of K2NaScF6:Yb/Er and subsequent crystallization of KSc2F7:Yb/Er during the opposite conversion process. Possible chemical reaction mechanisms were further developed to elucidate the interconversion details. Meanwhile, the variation of the upconversion luminescence such as emission intensity, red to green ratio, and lifetime is interpreted to monitor the conversion progress at corresponding stages, which is highly consistent with the scenario discussed above.

Insights into the growth mechanism of REF3 (RE = La-Lu, Y) nanocrystals: hexagonal and/or orthorhombic.

The synthesis of REF3 (RE = La-Lu, Y) nanocrystals with controlled phase structures has so far remained a challenge. Herein we have developed a one-for-all synthetic procedure that allows the successful synthesis of REF3 nanocrystals in a controlled manner. Experimental results showed that the radius of RE ions determines the phase structure: pure hexagonal REF3 (RE = La-Eu), a mixture of hexagonal and orthorhombic REF3 (RE = Gd), and pure orthorhombic REF3 (RE = Tb-Lu, Y) nanocrystals are obtained along with the decrease of the ionic radius. As Gd is positioned exactly in the middle of the lanthanides row, GdF3 nanocrystals were used as a model to further investigate how the molar ratio of F- : Gd3+, the doping of RE ions with different ionic radii, and the doping concentration of certain RE ions affects the crystal structure of the final product.

Coordination and supramolecular assembly of {Cd2Ge8V12O48} building block and cucurbit[6] to form rotaxane-shaped hybrids.

Assembly of cucurbit[6] and a {Cd2Ge8V12O48} cluster produced two rotaxane-shaped and polyrotaxane-shaped solids by changing the ratio of starting precursors in the system. The high oxygen density of the polyoxoanion surface provides active sites to extend a single rotaxane-shaped hybrid 1 to a 1D polyrotaxane-shaped hybrid 2. This construction strategy may afford an entirely new methodology for polyoxometalate-based hybrid chemistry.

Polyoxovanadate-based organic-inorganic hybrids: from {V5O9Cl} clusters to nanosized octahedral cages.

Three polyoxovanadate-based metal-organic polyhedra (denoted as VMOP-1, -2, and -3), adopting isostructural discrete octahedral cage geometries, were successfully synthesized under solvothermal conditions. These structures are all built up from the same pentavanadate {V5O9Cl} cluster connected by linear bidentate ligands (H2L1 = H2BDC, H2L2 = H2BDC-NH2, H2L3 = H2BDC-Br), respectively.

Steam-Assisted Synthesis of an Extra-Stable Polyoxometalate-Encapsulating Metal Azolate Framework: Applications in Reagent Purification and Proton Conduction.

Different from the conventional synthesis approaches, such as hydrothermal or solvothermal synthesis, a porous metal azolate framework encapsulating Keggin-type [SiW12 O40 ](4-) anions was prepared by an environmentally friendly, low-cost, and highly efficient steam-assisted conversion method for the first time. The nanosized polyoxometalates as a template were encapsulated by a zeotype 6(4) 4(8) cage constructed by 28 nuclear zinc atoms connected through 32 Trz ligands. The obtained composite exhibits excellent thermal and chemical stability; meanwhile, its special ability to selectively absorb water from alcohols makes it efficiently separate water from analytically pure ethanol, with the result that water content decreases from 0.23 to 0.05 wt %, which is superior to the standard of chromatographic grade ethanol (<0.1 wt %). Besides, alternating current (ac) impedance experiments also reveal that the hybrid is a kind of proton conductive material.

A Stable Polyoxometalate-Pillared Metal-Organic Framework for Proton-Conducting and Colorimetric Biosensing.

A stable metal-organic framework pillared by Keggin-type polyoxometalate, Cu6 (Trz)10 (H2O)4 [H2 SiW12 O40 ]⋅8 H2O (Trz=1,2,4-triazole) (1), has been prepared under hydrothermal condition. The 2D layer structure with a 22-member ring was formed by Cu(2+) ions, which are connected with each other via the Trz ligands on the ab plane. Thus, the 2D layers are further interconnected through Keggin polyoxoanions to generate a 3D porous network with a small 1D channel. Moreover, the presence of polyoxoanions make it exhibit selective adsorption of water and proton-conducting properties. Additionally it showed efficient intrinsic peroxidase-like activity, providing a simple and sensitive colorimetric assay to detect H2O2 .

Self-assembled arrays of polyoxometalate-based metal-organic nanotubes for proton conduction and magnetism.

The first polyoxometalate-based metal-organic nanotube constructed via covalent bonds has been synthesized. POM anions stick the metal-organic nanotubes to build 3D nanotubular arrays. The stability, magnetic and proton conducting properties are investigated.

pH-controlled and sulfite anion-directed assembly of a family of cerium(III)-containing polyoxotungstates clusters.

A versatile one-pot strategy was employed to synthesize five cerium(III)-containing polyoxotungstate nanoclusters through pH-controlled and sulfite anion-directed assembly: [C2H8N]3Na7[Ce2(H2O)6W22O72(OH)4]·20H2O (1) at pH 5.0; [C2H8N]8Na16[Ce4(H2O)12W44O144(OH)12]·23H2O (2) at pH 4.5; [C2H8N]2Na4Ce2[Ce2(H2O)10W28O92(OH)2]·27H2O (3) at pH 2.8-3.3; [C2H8N]2Na7[{α-SW7O28}{Ce2(H2O)6}(W3O6){α-SW9O32}{α-SW9O31(OH)}]·18H2O (4) at pH 2.5; [C2H8N]2Na18[Ce2(H2O)9W36O110(OH)12]2·30H2O (5) at pH 1.5. These compounds were characterized by single-crystal X-ray structure analysis, IR spectroscopy, thermogravimetric (TG) analysis, X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Moreover, their electrochemical properties were investigated. Single-crystal X-ray structure analysis revealed that 1 and 2 were di- and tetra-cerium(III)-bridged polyoxotungstates, constructed from two different types of lacunary {W11} units. 3 composed of the well-known cerium(III)-stabilized {W28} unit and organic amine-sodium-cerium cations, was isolated in the pH range 2.8-3.3. In this reaction system, the SO3(2-) anion acted as a heteroanion template at a lower pH 2.5. 4 was isolated by the combination of cerium(III) centers and SO3(2-) heteroanion template, which is the first lanthanide-containing polyoxotungstates with sulfur heteroatoms, and the 4f metal cerium(III) centers in 4 both have eight-coordinated modes and the SO3(2-) heteroanion templates display µ7 and µ9 coordination modes. At a much lower pH 1.5, the polyanion of 5 was obtained, two triangular-shaped {W36} subunits were bridged by the cerium(III) ions, resulting in the largest lanthanide-containing iso-polyoxotungstates known to date.

Iodine-templated assembly of unprecedented 3d-4f metal-organic frameworks as photocatalysts for hydrogen generation.

Unprecedented 3d-4f MOFs encapsulating infinite linear polyiodide chains were firstly reported using iodine molecules as a versatile precursor template. They possess high framework stability in acid/base aqueous solutions. The kinetics of iodine molecule release/recovery and UV-light photocatalytic H(2) evolution activities were investigated.