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A class of novel multifunctional hybrids assembled by lanthanide polyoxometalates, ionic liquid and lanthanide complexes were prepared through the reactions of ion exchange and coordination in mild conditions. These hybrids possess two luminescence centers, one is lanthanide polyoxometalates ([EuW10O36]9− or [TbW10O36]9−), the other is lanthanide complexes of 1,10-phenanthroline (phen) (or 2,2′-bipyridine (bpy)) and ionic liquid (1-methyl-3-propionic imidazole unit). Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD) analysis, thermo-gravimetric analysis (TGA), UV/vis diffuse reflectance spectra and photoluminescent properties are utilized to characterize these hybrid materials. The results reveal that all hybrids possess amorphous microstructures and are composed of inorganic polyoxometalates and lanthanide nitrate through chemical bonds. Most hybrids exhibit outstanding luminescent properties such as high quantum efficiency and long lifetimes. Moreover, the luminescent color of them can be tuned and even the white luminescence can be integrated. [ABSTRACT FROM AUTHOR]

Highlights: [•] Novel linkages of ionic liquid. [•] New lanthanide hybrids of mesoporous silica with POMs. [•] Luminescence color integration. [ABSTRACT FROM AUTHOR]

In this paper, we put forward a strategy to assemble a novel series of multi-component photofunctional hybrid materials (named as Eu-Si-P1(2,3)) centered with europium polyoxometalates (Na9EuW10O36·32H2O, abbreviated as EuW10) and polyester modified silane (P1-Si, P2-Si, P3-Si, P1 = poly glycohol, P2 = bis(2-hydroxyethyl)ether, P3 = 2-hydroxyethyl methacrylate) through an ionic liquid compound (1-methyl-3-(trimethoxysilylpropyl) imidazolium chloride, IM+Cl−) as the double functional linker. Furthermore, using Pluronic P123 surfactant as a template to control the sol–gel process of organically modified siloxane precursors, Eu-SBA15-P1(2,3) hybrids with mesoporous silica are constructed correspondingly. The results reveal that Eu-Si-P1(2,3) hybrids present the lower red/orange intensity ratio, longer lifetime and higher quantum yield than Eu-SBA15-P1(2,3) hybrids. The luminescent lifetime and quantum efficiency of Eu-Si-P1(2,3) hybrids are comparable with EuW10 compounds in spite of their low concentration of photoactive EuW10, which is important for practical applications. The CIE chromatic coordinates of some systems are close to the cool-white region and can be expected to be utilized as cool white lighting (close to sunlight). [ABSTRACT FROM AUTHOR]

[Display omitted] • The in-situ confined growth of CsPbX 3 was achieved in a hierarchically porous MOF. • A one-step perovskite precursor-impregnation approach was demonstrated. • The nanoconfined CsPbX 3 show bright luminescence and enhanced stability. • A primary WLED device showing a NTSC value of 125% was fabricated. Confining metal-halide perovskites within MOF hosts not only protects them from exterior environment stimulation and isolates them from each other without aggregation, but also enables a variety of new features and applications. In this work, a hierarchically porous MOF host was firstly explored for in-situ confined growth of CsPbX 3 perovskite nanocrystallites (PNCs). Compared with the previously used microporous MOF matrixes, this hierarchically porous MOF not only enables the impregnation of perovskite precursors in one step, but also allows more facile diffusion of the reactants, thus giving rise to high loading capacities and uniform distribution of CsPbX 3 perovskites. The MOF matrix serves as both template to guide the confined growth of monodispersed CsPbX 3 PNCs and encapsulation to enhance the stability of CsPbX 3 PNCs. The obtained CsPbX 3 @MOF nanocomposites show bright luminescence and good resistance to ambient moisture, UV light irradiation, and anion-exchange. By integrating the green-emitting CsPbBr 2 I@MOF and red-emitting CsPbI 3 @MOF nanocomposites with a commercial blue InGaN LED chip, we fabricate a primary WLED showing a NTSC value of 125% and Rec. 2020 of 93%, which highlights the potential in backlight display. [ABSTRACT FROM AUTHOR]

Given its wide application ranges, dielectric capacitors have garnered extensive attentions. However, due to the excessive premature agglomeration of free electrons, capacitors with nanocomposites as dielectrics fail to attain high breakdown strength (E b), and thereby constrain their ability to achieve superior energy storage performances. To alleviate the effects of free electrons and secondary impact-ionized electrons (SIE) on E b and leakage currents, here, a novel organic-inorganic core–shell Ni(OH) 2 @PDI (N@P) nanofiller with opposite double-PN-junction was well-designed and successfully synthesized by coating p-typed Ni(OH) 2 nanosheets with n-typed perylene diimide (PDI). It could reduce free electron kinetic energy and mitigate SIE amounts regardless of the applied electric field direction. Furthermore, PDI, as an organic compound, can uniformly and densely coat onto surfaces of 2D Ni(OH) 2 , as well as enhance compatibilities between Ni(OH) 2 and matrix, and thereby reducing structure defects at their interfaces. Last but not the least, Ni(OH) 2 nanosheets also contribute to E b improvement via acting as scattering centers. Experimental and simulation results concurrently affirmed positive influences of organic-inorganic N@P nanofillers on discharge energy density (U d) and efficiency (η) of P(VDF-HFP)-based (PVH-based) nanocomposites. Remarkably, 1.3 vol% N@P/PVH achieves a high U d of 21.7 J/cm3 and η of 81.2 % under 569.0 MV/m. More importantly, it maintains an excellent energy storage performance throughout 104 cyclic tests. This study presents a valid strategy for concurrently improving U d and η of polymer-based nanocomposites. [ABSTRACT FROM AUTHOR]

Dipicolinic acid (DPA) can serve as a convenient biomarker for Bacillus anthracis, which is an extremely hazardous pathogen and can be used as a biological weapon. Herein, we demonstrate a ratiometric luminescent sensor of DPA based on a dual-emissive MOF hybrid, which is developed by encapsulation of Tb3+ cations into an anionic MOF through a cation exchange process. The Tb3+@MOF hybrid well inherits the intrinsic ligand emission of the host framework and the Tb3+ emission. The parent framework can function as a host matrix to sensitize and protect the emission of incorporated Tb3+. The Tb3+ emission within the MOF hybrid is significantly enhanced in the presence of DPA molecules owing to the occurrence of antenna sensitization upon the formation of the Tb–DPA complex, while the ligand emission is insensitive to DPA. This unique ratiometric luminescence response of the Tb3+@MOF hybrid towards DPA can be exploited for sensitive self-calibrated detection of DPA. The Tb3+@MOF sensor shows a fast response rate, high sensitivity and selectivity with a limit of detection of 3.6 nM. Besides, the feasibility of this sensor operating in real samples is demonstrated by the good recovery of DPA in human serum. The present study provides a promising luminescent platform for routine analysis of an anthrax biomarker. [ABSTRACT FROM AUTHOR]

In this work, dual-responsive luminescent Her@Zn-Bim hybrids are developed by herniarin (Her) dye encapsulation engineering within a layered host MOF (Zn-Bim). The pore confinement effect of the Zn-Bim host effectively isolates the guest dye molecules, therefore affording bright blue dye emission for Her@Zn-Bim hybrids. Upon exposure to tetracycline antibiotics (TCs), the hybrid undergoes a significant quenching of the blue emission, concurrent with the appearance of a distinct green emission. This dual-emission response is very fast and sensitive, facilitating real-time ratiometric detection of TCs with a low limit of detection of 7.81 nM. Notably, the ratiometric luminescence response manifests as a readily observable blue-to-green color switching, enabling straightforward and colorimetric visualization of TCs. Visual and semiquantitative monitoring of TCs is achieved using a readily available smartphone installed with a color-analysis app. Furthermore, in conjunction with principal component analysis, the Her@Zn-Bim hybrids demonstrate efficient discrimination of four TCs with high structural and chemical similarities, even in complex mixture systems. The mechanisms underlying the luminescent responses of the hybrids towards TCs are carefully elucidated. These hybrid sensors, featuring high sensitivity, fast response, colorimetric visualization, and precise discrimination capability, hold promising potential for practical applications in sensing TCs. [Display omitted] • Dual-responsive luminescent dye@MOF hybrids are developed by dye encapsulation engineering. • The hybrids show dual-emission responses and blue-to-green color switching towards tetracyclines. • The dual-emission responses are very fast and sensitive. • Ratiometric trace detection and real-time colorimetric visualization of tetracyclines are achieved. • Effective discrimination among four tetracyclines is also accomplished when coupled with PCA. [ABSTRACT FROM AUTHOR]

[Display omitted] • First systematic review on the stimuli‐responsive luminescent MOFs for anticounterfeiting. • The responsive mechanisms toward various stimulus are discussed. • The implementation strategies for advanced anti‐counterfeiting are presented. • Challenges and prospects of anticounterfeiting based on responsive luminescent MOFs are discussed. Smart stimuli-responsive luminescent metal–organic frameworks (MOFs), combining the unique advantages and exciting application prospects, have gained booming development in recent years. The powerful capability to respond the external chemical or physical stimuli through various manners makes them particularly attractive in anti-counterfeiting technologies. This review aims at the recent progress of the stimuli-responsive luminescent MOF materials for advanced anti-counterfeiting technologies. The representative types of stimuli, such as light, temperature, solvent, pH, ion are summarized. In addition, the responsive luminescence and mechanisms, and the implementation strategies for advanced anti-counterfeiting are discussed. We also briefly present the current challenges and future perspectives of stimuli-responsive luminescent MOF materials for anticounterfeiting application. We hope this review would provide some new insights and guidelines for the design and engineering of novel stimuli-responsive luminescent MOF materials for advanced anticounterfeiting and information encryption. [ABSTRACT FROM AUTHOR]

[Display omitted] The development of efficient and stable white-light emissive materials is highly desirable in displays and solid-state lighting. Here we present a high-quality white-light emitter based a dual-emitting MOF hybrid, which is achieved by dye encapsulation engineering within a robust Zr-MOF (PCN-128W) containing a highly luminescent tetraphenylethylene-based ligand. The pore confinement effect well isolates the incorporated dye molecules (trans-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide (DSM)) and therefore suppress the aggregation caused luminescence quenching. The dye emission is mainly sensitized by PCN-128W host through Förster resonance energy transfer (FRET), and the FRET process is incomplete, thus enabling the hybrid to feature dual emissions upon a single excitation. The emission color of DSM@PCN-128W hybrid can be systematically tuned from blue to white, and to orange by regulating the dye encapsulation content. A broad white-light emission with a considerably high quantum yield (21.2%) is obtained in the case of dye contents of 0.15 wt%. The luminescence of DSM@PCN-128W hybrid is stable in ambient air for over 1 month, and show good resistance to continuous UV light irradiation, owing to the protective MOF Matrix that largely inhibits the UV exposure to dye molecules. What's more, by combining DSM@PCN-128W with a commercial UV LED chip, we fabricate a white-light emitting prototype device showing CIE chromaticity coordinates of (0.34, 0.33), a CRI of 79.1, and a CCT of 5525 K. [ABSTRACT FROM AUTHOR]

Spinel LiNi0.5Mn1.5O4 (LNMO) is a promising cathode candidate for the next‐generation high energy‐density lithium‐ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site‐selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd3‾ m structure. This site‐selective doping not only suppresses unfavorable two‐phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg‐doped LNMOs exhibit extraordinarily stable electrochemical performance in both half‐cells and prototype full‐batteries with novel TiNb2O7 counter‐electrodes. This work pioneers an atomic‐doping engineering strategy for electrode materials that could be extended to other energy materials to create high‐performance devices. [ABSTRACT FROM AUTHOR]

Spinel LiNi0.5Mn1.5O4 (LNMO) is a promising cathode candidate for the next‐generation high energy‐density lithium‐ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site‐selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd3‾ m structure. This site‐selective doping not only suppresses unfavorable two‐phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg‐doped LNMOs exhibit extraordinarily stable electrochemical performance in both half‐cells and prototype full‐batteries with novel TiNb2O7 counter‐electrodes. This work pioneers an atomic‐doping engineering strategy for electrode materials that could be extended to other energy materials to create high‐performance devices. [ABSTRACT FROM AUTHOR]

1-Hydroxypyrene (1-HP) is a urinary metabolite of polycyclic aromatic hydrocarbons (PAHs), and can function as a convenient biomarker for human intoxication of PAH carcinogens. The development of simple 1-HP sensors with high sensitivity and fast response is highly desirable. Herein, we demonstrate that a robust microcrystalline MOF with fluorescent pyrene cores, NU-1000, exhibits sensitive luminescence detection of urinary 1-HP. The pyrene core within NU-1000 behaves as the signal converter, whose luminescence is significantly quenched upon coming into contact with 1-HP owing to the efficient π–π charge transfer interactions between highly conjugated 1-HP and pyrene cores in NU-1000. The pore confinement effect of the molecular-sized channel of NU-1000 facilitates the preconcentration of 1-HP within NU-1000, which makes 1-HP contact with NU-1000 more sufficient therefore enhancing the detection efficiency. The charge transfer-related quenching mechanism is elucidated by diffuse-reflectance UV-vis and electron paramagnetic resonance (EPR) measurements, and a radical pair state is observed in NU-1000 upon accommodation of 1-HP. This work provides important insights into the development of MOF-based luminescent sensors for 1-HP, and should stimulate further studies toward designing more efficient MOFs with highly conjugated luminescent cores for 1-HP sensing. [ABSTRACT FROM AUTHOR]

Antibiotic tetracycline (TC) is a sort of main contaminates in water, and of adverse effect on ecosystems and human health. The development of simple and efficient methods for both detection and removal of TC in water is highly desirable but remains challenging. Herein, a dual-functional platform for detection and removal of antibiotic tetracycline (TC) is developed by a highly stable luminescent zirconium-based MOF (PCN-128Y). The detection is based on the efficient luminescence quenching of the PCN-128Y toward TC. Theoretical/experimental studies reveal that the luminescence quenching can be attributed to a combined effect of the strong absorption of TC at the excitation wavelength and the photo-induced electron transfer process from the ligand of PCN-128Y to TC. The strong cheating metal-ligand bonding between Zr 6 nodes and TC through solvent-assisted ligand incorporation is suggested to mainly account for the high adsorption capability of PCN-128Y toward TC in water. The preconcentration of TC within the pores of PCN-128Y induced by the adsorption process makes TC contact with the framework more sufficient, thus significantly enhances the efficiency of TC sensing. This work is the first example demonstrating that MOF materials can integrate the functions of detection and removal of antibiotic TC in water, which highlights the opportunity of luminescent MOFs in the application of wastewater treatment. [ABSTRACT FROM AUTHOR]

Luminescent MOF materials with tunable emissions and energy/charge transfer processes have been extensively explored as ratiometric temperature sensors. However, most of the ratiometric MOF thermometers reported thus far are based on the MOFs containing photoactive lanthanides, which are potentially facing cost issue and serious supply shortage. Here, we present a ratiometric luminescent thermometer based on a dual-emitting lanthanide-free MOF hybrid, which is developed by encapsulation of a fluorescent dye into a robust nanocrystalline zirconium-based MOF through a one-pot synthesis approach. The structure and morphology of the hybrid product was characterized by Powder X-ray diffraction (PXRD), N 2 adsorption-desorption measurement and Scanning electron microscopy (SEM). The pore confinement effect well isolates the guest dye molecules and therefore suppresses the nonradiative energy transfer process between dye molecules. The incorporated dye emission is mainly sensitized by the organic linkers within MOF through fluorescence resonance energy transfer. The ratiometric luminescence of the MOF hybrid shows a significant response to temperature due to the thermal-related back energy transfer process from dye molecules and organic linkers, thus can be exploited for self-calibrated temperature sensing. The maximum thermometric sensitivity is 1.19% °C −1 in the physiological temperature range, which is among the highest for the ratiomtric MOF thermometers that operating in 25–45 °C. The temperature resolution is better than 0.1 °C over the entire operative range (20–60 °C). By integrating the advantages of excellent stability, nanoscale nature, and high sensitivity and precision in the physiological temperature range, this dye@MOF hybrid might have potential application in biomedical diagnosis. What’ more, this work has expanded the possibility of non-lanthanide luminescent MOF materials for the development of ratiometric temperature sensors. [ABSTRACT FROM AUTHOR]

Core-shell Mn 3 O 4 /carbon (Mn 3 O 4 @C) hybrid fiber are synthesized by encapsulating Mn 3 O 4 nanoparticles (NPs) in the hollow carbon fibers (Mn 3 O 4 @HCFs) according to the coaxial electrospinning technique. As the aqueous Zinc ion battery (ZIBs) cathode, the well-defined Mn 3 O 4 @HCFs with 12.7 wt % carbon exhibits superior rate capability (215.8 and 115.7 mAh g−1 at 0.3 and 2.0 A g−1, respectively) and excellent cycling stability (225 mAh g−1 remaining at the current density of 400 mA g−1 after 1300 cycles). The outstanding electrochemical performances are attributed to the core-shell structure of the Mn 3 O 4 @HCFs with much void spaces. The carbon framework on the surface of the Mn 3 O 4 NPs can not only relieve the volume expansion of Mn 3 O 4 during the discharging, but also optimize the electron transportation inside these fibers for the electrode. Furthermore, the amorphous carbon shell could also reduce the dissolution of the Mn 3 O 4 NPs during cycling. This work will provide a new pathway of a technique for enhancing the manganese-based cathode materials for the high-powered rechargeable aqueous ZIBs. [ABSTRACT FROM AUTHOR]