Dual Phase‐Controlled Synthesis of Uniform Lanthanide‐Doped NaGdF4 Upconversion Nanocrystals Via an OA/Ionic Liquid Two‐Phase System for In Vivo Dual‐Modality Imaging

A novel OA/ionic liquid two‐phase system combining the merits of thermal decomposition method, the IL‐based strategy, and the two‐phase approach is introduced to synthesize high‐quality lanthanide‐doped NaGdF₄ upconversion nanocrystals with different crystal‐phases in OA‐phase and IL‐phase through a one‐step controllable reaction. Oil‐dispersible cubic‐phase NaGdF₄:Yb, Er (Ho, Tm) nanocrystals with ultra‐small size (～5 nm) and monodispersity are obtained in the OA phase of the two‐phase system via an IL‐based reaction. More importantly, water‐soluble hexagonal‐phase NaGdF₄:Yb, Er nanocrystals are obtained in the same system simply by adopting an extremely facile method to complete the dual phase‐transition (crystal‐phase transition and OA‐phase to IL‐phase transition) simultaneously. The synthesized lanthanide‐doped NaGdF₄ upconversion nanocrystals are effective for dual‐mode UCL imaging and CT imaging in vivo.     

Ordered Mesoporous Metastable α‐MoC1−x with Enhanced Water Dissociation Capability for Boosting Alkaline Hydrogen Evolution Activity

The sluggish reaction kinetics of the alkaline hydrogen evolution reaction (HER) remains an important challenge for water–alkali electrolyzers, which originates predominantly from the additional water dissociation step required for the alkaline HER. In this work, it is demonstrated theoretically and experimentally that metastable, face‐centered‐cubic α‐MoC_1?x phase shows superior water dissociation capability and alkaline HER activity than stable, hexagonal‐close‐packed Mo₂C phase. Next, high surface area ordered mesoporous α‐MoC_1?x (MMC) is designed via a nanocasting method. In MMC structure, the α‐MoC_1?x phase facilitates the water dissociation reaction, while the mesoporous structure with high surface area enables a high dispersion of metal NPs and efficient mass transport. As a result, Pt nanoparticles (NPs) supported on MMC (Pt/MMC) show substantially enhanced alkaline HER activity in terms of overpotentials, Tafel slopes, mass and specific activities, and exchange current densities, compared to commercial Pt/C and Pt NPs supported on particulate α‐MoC_1?x or β‐Mo₂C. Notably, Pt/MMC shows very low Tafel slope of 30 mV dec^–1, which is the lowest value among the reported Pt‐based alkaline HER catalysts, suggesting the critical role of MMC in enhancing the HER kinetics. The promotional effect of MMC support in the alkaline HER is further demonstrated with an Ir/MMC catalyst.     

Visible and NIR Upconverting Er3+–Yb3+ Luminescent Nanorattles and Other Hybrid PMO‐Inorganic Structures for In Vivo Nanothermometry

Lanthanide‐doped luminescent nanoparticles are an appealing system for nanothermometry with biomedical applications due to their sensitivity, reliability, and minimal invasive thermal sensing properties. Here, four unique hybrid organic–inorganic materials prepared by combining β‐NaGdF₄ and PMOs (periodic mesoporous organosilica) or mSiO₂ (mesoporous silica) are proposed. PMO/mSiO₂ materials are excellent candidates for biological/biomedical applications as they show high biocompatibility with the human body. On the other hand, the β‐NaGdF₄ matrix is an excellent host for doping lanthanide ions, even at very low concentrations with yet very efficient luminescence properties. A new type of Er³⁺–Yb³⁺ upconversion luminescence nanothermometers operating both in the visible and near infrared regime is proposed. Both spectral ranges permit promising thermometry performance even in aqueous environment. It is additionally confirmed that these hybrid materials are non‐toxic to cells, which makes them very promising candidates for real biomedical thermometry applications. In several of these materials, the presence of additional voids leaves space for future theranostic or combined thermometry and drug delivery applications in the hybrid nanostructures.     

Hydrothermal Synthesis and Luminescent Properties of BiPO4:Eu3+ Phosphors

In this study, BiPO₄:Eu³⁺ phosphors were synthesized by a facile hydrothermal route at different temperatures. The BiPO₄:Eu³⁺ particles were characterized by x-ray powder diffraction (XRD), infrared spectra, and luminescence spectroscopy. The XRD results reveal that the BiPO₄:Eu³⁺ particles present different phases for different hydrothermal temperatures. It is found that a hexagonal phase is formed at 100°C, which transforms to a low-temperature monoclinic phase (MP) when the hydrothermal temperature is increased to 150°C. This low-temperature MP transforms to high-temperature MP when the temperature is increased beyond 200°C. The luminescent properties of the BiPO₄:Eu³⁺ particles were studied using an excitation wavelength of 270 nm. The emission spectra display the bands associated with the ⁵D₀ → ⁷F _J (J = 1, 2, 3, and 4) electronic transitions of the Eu³⁺ cations. The intensity of the emission spectra increases with increasing hydrothermal temperature. These results demonstrate that BiPO₄:Eu³⁺ with different phases can be obtained through the hydrothermal method, which may enrich the solution chemistry for preparation of advanced materials with tailored functionality.     

Bright Blue Photo‐ and Electroluminescence from Eu2+‐Doped GaN/SiO2 Nanocomposites

In this article we demonstrate the synthesis of Eu²⁺‐doped GaN/SiO₂ nanocomposites using a simple solid state reaction and their use in light‐emitting devices. The nanocomposite exhibits a bright blue luminescence when excited in the UV region (quantum yield = 23 %). The origin of the blue emission is attributed to the presence of europium ions in the +2 oxidation state in the GaN/SiO₂ nanocomposites. Analysis of the EPR spectrum of europium‐doped GaN/SiO₂ nanocomposites confirms the existence of Eu²⁺ in the nanocomposites. Various control experiments show that the blue emission arises from these europium ions and that the interface of GaN and silica plays a crucial role. The Eu²⁺‐doped GaN/SiO₂ nanocomposite also exhibits a bright blue electroluminescence. Furthermore, the nanocomposites can be coated with a polymer to tune their dispersibility in organic medium.     

Electrospinning Preparation and Drug‐Delivery Properties of an Up‐conversion Luminescent Porous NaYF4:Yb3+, Er3+@Silica Fiber Nanocomposite

Up‐conversion (UC) luminescent porous silica fibers decorated with NaYF₄:Yb³⁺, Er³⁺ nanocrystals (NCs) (denoted as NaYF₄:Yb³⁺, Er³⁺@silica fiber) are prepared by the electrospinning process using cationic surfactant P123 as a template. Monodisperse and hydrophobic oleic acid capped β‐NaYF₄: Yb³⁺, Er³⁺ NCs are prepared by thermal decomposition methodology. Then, these NCs are transferred into aqueous solution by employing cetyltrimethylammonium bromide (CTAB) as secondary surfactant. The water‐dispersible β‐NaYF₄:Yb³⁺, Er³⁺ NCs are dispersed into precursor electrospinning solution containing P123 and tetraethyl orthosilicate (TEOS), followed by preparation of precursor fibers via electrospinning. Finally, porous α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites are obtained after annealing the precursor fibers containing β‐NaYF₄:Yb³⁺, Er³⁺ at 550 °C. The as‐prepared α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber possesses porous structure and UC luminescence properties simultaneously. Furthermore, the obtained nanocomposites can be used as a drug delivery host carrier and drug storage/release properties are investigated, using ibuprofen (IBU) as a model drug. The results indicate that the IBU–loaded α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites show UC emission of Er³⁺ under 980 nm NIR laser excitation and a controlled release property for IBU. Meanwhile, the UC emission intensity of IBU–α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber system varies with the released amount of IBU.     

Preparation of Tortuous 3D γ‐CsPbI3 Films at Low Temperature by CaI2 as Dopant for Highly Efficient Perovskite Solar Cells

Inorganic cubic CsPbI₃ perovskite (α‐CsPbI₃) has been widely explored for perovskite solar cells (PSCs) due to its thermal stability and suitable bandgap of 1.73 eV. However, α‐CsPbI₃ usually requires high synthesis temperatures (>320 °C). Additionally, it usually undergoes phase transition to the nonperovskite structure phase (β‐CsPbI₃), which results in poor photoelectric performance in devices. In this study, it is first found that the tortuous 3D CsPbI₃ phase (γ‐CsPbI₃) can be prepared and used for PSCs by solution process without any additive at low temperature (60 °C). The γ‐CsPbI₃ exhibits suitable bandgap of 1.75 eV and favorable photoelectric properties. However, γ‐CsPbI₃ is a metastable phase and easily transforms into β‐CsPbI₃ in ambient moisture. In order to improve the stability of γ‐CsPbI₃, calcium ions (Ca²⁺) with a relatively small radius of 100 pm are used to partially substitute lead ions (119 pm). This research proves that Ca²⁺ can effectively improve the stability of the γ‐CsPbI₃ at room temperature. By optimizing the doping concentration of Ca²⁺ (CsPb_1?xCa_xI₃, x is from 0% to 2%), the Ca²⁺‐doped γ‐CsPbI₃ PSCs achieve a hysteresis‐free J–V curve and a maximum power conversion efficiency (PCE) of 9.20%.     

Controlled Growth of Porous α‐Fe2O3 Branches on β‐MnO2 Nanorods for Excellent Performance in Lithium‐Ion Batteries

Hierarchical nanocomposites rationally designed in component and structure, are highly desirable for the development of lithium‐ion batteries, because they can take full advantages of different components and various structures to achieve superior electrochemical properties. Here, the branched nanocomposite with β‐MnO₂ nanorods as the back‐bone and porous α‐Fe₂O₃ nanorods as the branches are synthesized by a high‐temperature annealing of FeOOH epitaxially grown on the β‐MnO₂ nanorods. Since the β‐MnO₂ nanorods grow along the four‐fold axis, the as‐produced branches of FeOOH and α‐Fe₂O₃ are aligned on their side in a nearly four‐fold symmetry. This synthetic process for the branched nanorods built by β‐MnO₂/α‐Fe₂O₃ is characterized. The branched nanorods of β‐MnO₂/α‐Fe₂O₃ present an excellent lithium‐storage performance. They exhibit a reversible specific capacity of 1028 mAh g^?1 at a current density of 1000 mA g^?1 up to 200 cycles, much higher than the building blocks alone. Even at 4000 mA g^?1, the reversible capacity of the branched nanorods could be kept at 881 mAh g^?1. The outstanding performances of the branched nanorods are attributed to the synergistic effect of different components and the hierarchical structure of the composite. The disclosure of the correlation between the electrochemical properties and the structure/component of the nanocomposites, would greatly benefit the rational design of the high‐performance nanocomposites for lithium ion batteries, in the future.     

Room‐Temperature Partial Conversion of α‐FAPbI3 Perovskite Phase via PbI2 Solvation Enables High‐Performance Solar Cells

The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI₃ hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI₃, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI₃, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI₂ into the α‐FAPbI₃ perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI₂ precursor from its different states are compared. α‐FAPbI₃ forms spontaneously and efficiently at room temperature from P₂ (ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI₂) to 17.23(±0.28)% (from solvated PbI₂) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA⁺ cation without the need for Cs⁺ or mixed halide formulation.     

Novel Red-Emitting Microwave-Assisted-Sintered LiSrPO4: Eu3+ Phosphors for Application in Near-UV White Light-Emitting Diodes

Novel red-emitting LiSr_1?x PO₄:xEu³⁺ phosphors with various concentrations (x = 0.03, 0.05, 0.07, 0.1) of Eu³⁺ ions were synthesized by microwave-assisted sintering at 1200°C for 3 h in air. The microstructural and luminescent characteristics of the LiSrPO₄:Eu³⁺ phosphors were investigated and are discussed here. x-Ray diffraction (XRD) results showed that the prepared LiSr_1?x PO₄:xEu³⁺ phosphors presented an impurity phase of Eu₂O₃ when the Eu³⁺ ions exceeded x = 0.05. Photoluminescence (PL) results showed a series of emission states ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁, ⁵D₀ → ⁷F₂, ⁵D₀ → ⁷F₃, and ⁵D₀ → ⁷F₄ (corresponding to the typical 4f → 4f intraconfiguration forbidden transitions of Eu³⁺) with a major emission peak at around 617 nm. The optimum concentration of Eu³⁺ for LiSr_1?x PO₄:xEu³⁺ prepared by microwave-assisted sintering was found to be 0.05. The lifetime values of LiSr_1?x PO₄:xEu³⁺ phosphors with doping concentrations of Eu³⁺ ions of 0.03, 0.05, 0.07, and 0.1 were found to be 3.32 ms, 3.30 ms, 2.84 ms, and 2.60 ms, respectively. Moreover, the chromaticity values (x, y) of all of the LiSr_1?x PO₄:xEu³⁺ phosphors were located in the red region (0.65, 0.34).     

Synthesis of Hexagonal Yb3+,Er3+‐Doped NaYF4 Nanocrystals at Low Temperature

Nanocrystals of NaYF₄ doped with Yb³⁺ and Er³⁺ are synthesized in oleylamine using Y₂(CO₃)₃, Yb₂(CO₃)₃, Er₂(CO₃)₃, Na₂CO₃, and NH₄F as precursors. In contrast to other starting materials normally used for such syntheses, these precursors react even at room temperature to form hexagonal‐phase (β‐phase) NaYF₄:Er,Yb nanoparticles. Cubic‐phase (α‐phase) NaYF₄:Yb,Er particles are formed only at elevated temperatures (>250 °C). The formation of the cubic phase at high temperatures can be suppressed by replacing pure oleylamine with oleic acid/oleylamine mixtures. Under optimized reaction conditions, particles with an average particle size of about 7 nm are generated in 84% yield. Heat treatment (30 min, 280 °C) of the particles significantly increases the luminescence efficiency. A transparent solution of the heat‐treated, nanometer‐sized phosphor in toluene shows intense visible light emission upon excitation in the near infrared.     

Patterning of YVO4:Eu3+ Luminescent Films by Soft Lithography

Ordered arrays of luminescent YVO₄:Eu³⁺ films with square (side length 19.17 ± 2.05 μm) and dot (diameter 11.20 ± 1.82 μm) patterns were fabricated by two kinds of soft lithography processes, namely, microtransfer molding (μTM) and microcontact printing (μCP), respectively. Both soft‐lithography processes utilize a PDMS elastomeric mold as the stamp combined with a Pechini‐type sol‐gel process to produce luminescent patterns on quartz plates, in which a YVO₄:Eu³⁺ precursor solution was employed as ink. The ordered luminescent YVO₄:Eu³⁺ patterns are revealed by optical micro­scopy and their microstructure, consisting of nanometer‐scale particles, is unveiled by scanning electronic microscopy (SEM) observations. Additionally, photoluminescence (PL) and cathodoluminescence (CL) were carried out to characterize the patterned YVO₄:Eu³⁺ samples. A strong red emission as a result of ⁵D₀–⁷F₂ transition of Eu³⁺ was observed under UV‐light or electron‐beam excitation, which implies that combining soft lithography with a Pechini‐type sol‐gel route has potential for fabricating rare‐earth luminescent pixels for next‐generation field‐emission display devices.     

Hydrothermal Synthesis of SrMoO4:Eu3+, Sm3+ Phosphors and Their Enhanced Luminescent Properties Through Energy Transfer

Eu³⁺ and Sm³⁺ co-doped SrMoO₄ phosphors have been successfully prepared via a simple surfactant-free hydrothermal method. The as-prepared phosphors present dumbbell-like agglomerates and comprise of many nanoparticles of 150–300 nm in diameter. Eu³⁺ and Sm³⁺ co-doped SrMoO₄ phosphors display all the characteristic excitations and emissions of Eu³⁺ and Sm³⁺. The introduction of Sm³⁺ can generate a strong excitation line at 403 nm, originating from the ⁶H_5/2 → ⁴K_11/2 transition of Sm³⁺, which significantly broadened the excitation region for matching the near ultraviolet light emitting diodes (～400 nm). And Sm³⁺ ions can transfer the absorbed energy to Eu³⁺ ions efficiently, so the intensity of the main emission peak at 614 nm due to ⁵D₀ → ⁷F₂ transition of Eu³⁺ are strengthened by the co-doping of Sm³⁺. The doping concentration of Eu³⁺/Sm³⁺ was optimized. In addition, the possible energy transfer mechanism has been investigated and is discussed in detail.     

Pressure‐Driven Eu2+‐Doped BaLi2Al2Si2N6: A New Color Tunable Narrow‐Band Emission Phosphor for Spectroscopy and Pressure Sensor Applications

A series of BaLi₂Al₂Si₂N₆ (BLASN): xEu²⁺ phosphors are successfully synthesized and their crystal structure and luminescence properties under varying hydrostatic pressures are reported herein. Structure variation is analyzed using in situ high‐pressure X‐ray diffraction and Rietveld refinements. Based on decay curves and Gaussian fitting of emission spectra, the presence of two photoluminescence centers is demonstrated. BaLi₂Al₂Si₂N₆: 0.01Eu²⁺ exhibits an evident peak position shift from 532 to 567 nm with an increase in pressure to ≈20 GPa. The possible factors and mechanisms for the variations are studied in detail. At a pressure of 16 GPa, BLASN: Eu²⁺ realizes a narrow yellow emission with a full width at half maximum of ≈70 nm. The addition of BLASN: Eu²⁺ (16 GPa) to the commercial white light‐emitting diodes combination consisting of an InGaN chip, β‐SiAlON: Eu²⁺, and red K₂SiF₆:Mn⁴⁺, can increase the color gamut by ≈15%, demonstrating the promising potential of pressure‐driven BLASN: Eu²⁺ for wide‐color gamut spectroscopy applications. Moreover, the emission shifts arising from pressure variation and the distinct color changes enable its potential utility as an optical pressure sensor; the material exhibits high pressure sensitivity (dλ/dP ≈ 1.58 nm GPa^?1) with the advantage of visualization.     

Energy transfer of Ce3+ → Eu2+ in the CaGa2S4 compound

Photoluminescence of CaGa₂S₄:Eu²⁺, CaGa₂S₄:Ce³⁺, and CaGa₂S₄:(Eu²⁺, Ce³⁺) is shown to be caused by intracenter transitions of Eu²⁺ and Ce³⁺ ions. It is ascertained that an energy transfer with an efficiency of 0.43 takes place from Ce³⁺ to Eu²⁺.     

Angular‐Shaped 4,9‐Dialkyl α‐ and β‐Naphthodithiophene‐Based Donor–Acceptor Copolymers: Investigation of Isomeric Structural Effects on Molecular Properties and Performance of Field‐Effect Transistors and Photovoltaics

Two angular‐shaped 4,9‐didodecyl α‐aNDT and 4,9‐didodecyl β‐aNDT isomeric structures have been regiospecifically designed and synthesized. The distannylated α‐aNDT and β‐aNDT monomers are copolymerized with the Br‐DTNT monomer by the Stille coupling to furnish two isomeric copolymers, PαNDTDTNT and PβNDTDTNT, respectively. The geometric shape and coplanarity of the isomeric α‐aNDT and β‐aNDT segments in the polymers play a decisive role in determining their macroscopic device performance. Theoretical calculations show that PαNDTDTNT possesses more linear polymeric backbone and higher coplanarity than PβNDTDTNT. The less curved conjugated main chain facilitates stronger intermolecular π–π interactions, resulting in more redshifted absorption spectra of PαNDTDTNT in both solution and thin film compared to the PβNDTDTNT counterpart. 2D wide‐angle X‐ray diffraction analysis reveals that PαNDTDTNT has more ordered π‐stacking and lamellar stacking than PβNDTDTNT as a result of the lesser curvature of the PαNDTDTNT backbone. Consistently, PαNDTDTNT exhibits a greater field effect transistor hole mobility of 0.214 cm² V^?1 s^?1 than PβNDTDTNT with a mobility of 0.038 cm² V^?1 s^?1. More significantly, the solar cell device incorporating the PαNDTDTNT:PC₇₁BM blend delivers a superior power conversion efficiency (PCE) of 8.01% that outperforms the PβNDTDTNT:PC₇₁BM‐based device with a moderate PCE of 3.6%.     

Synthesis of Luminescent ZrO2:Eu3+ Nanoparticles and Their Holographic Sub‐Micrometer Patterning in Polymer Composites

Here, the facile synthesis of fluorescent ZrO₂:Eu³⁺ nanoparticles with luminescence quantum yield of up to 8.7% that can be easily dispersed in organic solvents and utilized for the preparation of organic/inorganic volume holographic gratings is presented. The nanoparticles are prepared through a one‐step solvothermal process resulting in spherical particles with a mean size of 4 nm that were highly crystalline directly after the synthesis, without any need for calcination treatment. Detailed luminescence studies of the nanoparticles as a function of Eu³⁺ content demonstrate that the dopant concentration and its site symmetry play an important role in the emissive properties and lifetime of the luminescent centers. It is shown that the luminescence quantum yield of the colloidal ZrO₂:Eu³⁺ nanoparticles increases with dopant concentration up to a critical concentration of 11 mol% while the luminescence lifetime is shortened from 1.8 to 1.4 ms. Holographic photopolymerization of suitable monomer mixtures containing the luminescent nanoparticles demonstrated the ability to inscribe volume Bragg gratings (refractive index contrast n₁ up to 0.011) with light‐emissive properties, evidencing the high suitability of this approach for the fabrication of tailored nanomaterials for elaborate and demanding applications.     

Photoluminescence properties of YVO4:Eu3+,Ba2+ nanoparticles prepared by an ion exchange method

YVO₄:Ba²⁺ nanoparticles with a Ba²⁺ doping concentration x=0%, 1%, 3%, 5%, 7% and 9% were synthesized by a solvothermal method and then they were codoped with Eu³⁺ ions by an ion exchange method to form the YVO₄:Eu³⁺,Ba²⁺ nanoparticles. It was found that the photoluminescence intensity of the as-prepared YVO₄:Eu³⁺,Ba²⁺ nanoparticles steadily increased with x until x=7%, and then decreased for higher x. Thermal annealing resulted in considerable enhancement in their photoluminescence, and higher annealing temperature led to stronger photoluminescence enhancement. The emission intensity of the YVO₄:Eu³⁺,Ba²⁺ (x=7%) nanoparticles annealed at 500 °C was about 205% stronger than the sample without Ba²⁺ doping. Thermal annealing of the ion-exchanged YVO₄:Eu³⁺,Ba²⁺ nanoparticles at 500 °C and 700 °C resulted in photoluminescence enhancement of about 14 times and 27 times, respectively. The asymmetric ratio of Eu³⁺ in the ion-exchanged YVO₄:Eu³⁺,Ba²⁺ nanoparticles was found to increase after annealing.     

Green‐Chemical Synthesis of Ultrathin β‐MnOOH Nanofibers for Separation Membranes

Ultrathin β‐MnOOH nanofibers can be produced on a large scale via a green‐chemical method using an aqueous solution of very dilute Mn(NO₃)₂ and aminoethanol at room temperature. High‐magnification electron microscopy demonstrates that the β‐MnOOH nanofibers are 3–5 nm thin and up to 1 micrometer long and the nanofibers are parallel assembled into bundles with an average diameter of 25 nm. By a filtration process, ultrathin mesoporous membranes with strong mechanical, thermal, and chemical stabilities are prepared from the β‐MnOOH nanofiber bundles. The membranes can separate 10‐nm nanoparticles from water at a flux of 15120 L m^?2·h^?1·bar^?1, which was 2–3 times higher than that of commercial membranes with similar rejection properties. Based on the Young‐Laplace equation, β‐MnOOH nanofiber/polydimethylsiloxane composite membranes are developed through a novel downstream‐side evaporation process. From nanoporous to dense separation membranes can be achieved by optimizing the experimental conditions. The membranes show desirable separation performance for proteins, ethanol/water mixtures, and gases. The synthesis method of β‐MnOOH nanofibers is simple and environmentally friendly, and it is easily scalable for industry and applicable to other metal oxide systems. These composite membranes constitute a significant contribution to advanced separation technology.     

Novel Sol–Gel Nano‐Glass–Ceramics Comprising Ln3+‐Doped YF3 Nanocrystals: Structure and High Efficient UV Up‐Conversion

Transparent glass‐ceramics containing Ln³⁺‐doped YF₃ nanocrystals are successfully obtained under adequate thermal treatment of precursor sol–gel glasses for the first time, to the best of our knowledge. Precipitation of YF₃ nanocrystals is confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy images. An exhaustive structural analysis is carried out using Eu³⁺ and Sm³⁺ as probe ions of the final local environment in the nano‐structured glass–ceramic. Noticeable changes in luminescence spectra, related to relative intensity and Stark structure of band components, along with remarkably different lifetime values, allow us to discern between ions residing in precipitated YF₃ nanocrystals and those remaining in a glassy environment. A large fraction of optically active ions is efficiently partitioned into nanocrystals of small size, around 11 nm. Moreover, bright and efficient up‐conversion, including very intense high‐energy emissions in the UV range, due to 4‐ and 5‐infrared photon processes, are achieved in Yb³⁺–Tm³⁺ co‐doped samples. Up‐conversion mechanisms are analysed in depth by means of intensity dependence on sensitiser Yb³⁺ concentration and pump power.