Construction of Ketoenamine-Based Covalent Organic Frameworks with Electron-Rich Sites for Efficient and Rapid Removal of Iodine from Solution.

Porous covalent organic frameworks (COFs) have been widely used for the efficient removal of iodine from solution due to their abundance of electron-rich sites. In this study, two kinds of ketoenamine-based COFs, TpBD-(OMe)2 and TpBD-Me2, are successfully synthesized via Schiff base reaction under solvothermal conditions using 1, 3, 5-triformylphoroglucinol as aldehyde monomer, o-tolidine and o-dianisidine as amino monomers. The ability of TpBD-(OMe)2 and TpBD-Me2 to adsorb iodine in cyclohexane or aqueous solutions has been quantitatively analyzed and interpreted in terms of adsorption sites. TpBD-Me2 possesses two adsorption sites, -NH- and -C=O, and exhibits an adsorption capacity of 681.67 mg/g in cyclohexane, with an initial adsorption rate of 0.6 g/mol/min with respect to COF unit cell. The adsorption capacity of TpBD-(OMe)2 can be as high as 728.77 mg/g, and the initial adsorption rate of TpBD-(OMe)2 can reach 1.2 g/mol/min in the presence of oxygen atoms between the methyl group and the benzene ring. Compared with TpBD-Me2, the higher adsorption capacity and adsorption rate of TpBD-(OMe)2 towards iodine are not only reflected in organic solvents, but also in aqueous solutions. It is proven through X-ray photoelectron spectroscopy and Raman spectroscopy that iodine exists in the form of I2, I3-, and I5- within TpBD-(OMe)2 and TpBD-Me2 after adsorption. This work not only expands the application of COFs in the field of iodine adsorption, but also provides research ideas and important an experimental basis for the optimization of iodine adsorption sites.

Valence conversion and site reconstruction in near-infrared-emitting chromium-activated garnet for simultaneous enhancement of quantum efficiency and thermal stability.

Achievement of high photoluminescence quantum efficiency and thermal stability is challenging for near-infrared (NIR)-emitting phosphors. Here, we designed a "kill two birds with one stone" strategy to simultaneously improve quantum efficiency and thermal stability of the NIR-emitting Ca3Y2-2x(ZnZr)xGe3O12:Cr garnet system by chemical unit cosubstitution, and revealed universal structure-property relationship and the luminescence optimization mechanism. The cosubstitution of [Zn2+-Zr4+] for [Y3+-Y3+] played a critical role as reductant to promote the valence transformation from Cr4+ to Cr3+, resulting from the reconstruction of octahedral sites for Cr3+. The introduction of [Zn2+-Zr4+] unit also contributed to a rigid crystal structure. These two aspects together realized the high internal quantum efficiency of 96% and excellent thermal stability of 89%@423 K. Moreover, information encryption with "burning after reading" was achieved based on different chemical resistance of the phosphors to acid. The developed NIR-emitting phosphor-converted light-emitting diode demonstrated promising applications in bio-tissue imaging and night vision. This work provides a new perspective for developing high-performance NIR-emitting phosphor materials.

Multimode Luminescence Tailoring and Improvement of Cs2 NaHoCl6 Cryolite Crystals via Sb3+ /Yb3+ Alloying for Versatile Photoelectric Applications.

Lead-free halide double perovskites are currently gaining significant attention owing to their exceptional environmental friendliness, structural adjustability as well as self-trapped exciton emission. However, stable and efficient double perovskite with multimode luminescence and tunable spectra are still urgently needed for multifunctional photoelectric application. Herein, holmium based cryolite materials (Cs2 NaHoCl6 ) with anti-thermal quenching and multimode photoluminescence were successfully synthesized. By the further alloying of Sb3+ (s-p transitions) and Yb3+ (f-f transitions) ions, its luminescence properties can be well modulated, originating from tailoring band gap structure and enriching electron transition channels. Upon Sb3+ substitution in Cs2 NaHoCl6 , additional absorption peaking at 334 nm results in the tremendous increase of photoluminescence quantum yield (PLQY). Meanwhile, not only the typical NIR emission around 980 nm of Ho3+ is enhanced, but also the red and NIR emissions show a diverse range of anti-thermal quenching photoluminescence behaviors. Furthermore, through designing Yb3+ doping, the up-conversion photoluminescence can be triggered by changing excitation laser power density (yellow-to-orange) and Yb3+ doping concentration (red-to-green). Through a combined experimental-theoretical approach, the related luminescence mechanism is revealed. In general, by alloying Sb3+ /Yb3+ in Cs2 NaHoCl6 , abundant energy level ladders are constructed and more luminescence modes are derived, demonstrating great potential in multifunctional photoelectric applications.

Self-Doping Based Facet Junctions and Oxygen Vacancies in Ferroelectric Bi3TixNb2-xO9 Nanosheets for Boosting Photocatalytic Degradation and Antibacterial Activity.

Constructing facet junction in semiconductor photocatalysts has been demonstrated as an effective method to promote charge-carrier separation and suppress carrier recombination. Herein, we proposed a novel but facile self-doping strategy to regulate the crystal facet exposure ratio in ferroelectric Bi3TixNb2-xO9 single-crystalline nanosheets, thereby optimizing its facet junction effect. Through tuning the atomic ratio of Ti and Nb, the exposure ratio of {001} and {110} crystal planes in Bi3TixNb2-xO9 nanosheets can be delicately modulated, and more {110} facets were exposed with the increase of the Ti/Nb atomic ratio as evidenced by the X-ray diffraction and scanning electron microscopy results. A facet junction between {110} and {001} crystal planes was verified based on the density functional theory calculation and photodeposition experiment results. Photogenerated electrons tend to accumulate in {110}, while holes gathered in {001} crystal planes. Owing to the optimal facet junction effect, the sample of Ti1.05 shows the most efficient charge-carrier separation and transportation compared to Ti0.95 and Ti1.00 as supported by the photoluminescence, surface photovoltage, photoelectrochemistry, and electron paramagnetic resonance (EPR) results. In addition, the oxygen vacancy arising from the inequivalent substitution of Nb5+ by Ti4+ as proved by X-ray photoelectron spectroscopy and EPR results and the enhanced ferroelectricity supported by P-E loops can also assist charge-carrier separation and migration. Benefiting from these properties, Ti1.05 outperformed Ti0.95 and Ti1.00 in the photodegradation of organic dye and antibiotic molecules. Meanwhile, the excellent antibacterial activity of Ti1.05 under visible light was also demonstrated by the Escherichia coli sterilization experiment. This work not only presents a novel pathway to adjust the facet junction but also provides new deep insights into the crystal facet engineering in ferroelectrics as photocatalysts.

Tunable Dual Emission in Bi3+/Te4+-Doped Cs2HfCl6 Double Perovskites for White Light-Emitting Diode Applications.

Multicolor-emission-based single-phase white light derived from different luminescence centers is an effective way to manipulate the optical properties of halide perovskites. In this work, we developed a codoping strategy to incorporate Bi3+ and Te4+ emission centers into all-inorganic lead-free Cs2HfCl6 perovskite by a hydrothermal method. The as-prepared Bi3+/Te4+-doped Cs2HfCl6 microcrystals show bright blue (Bi3+), yellow (Te4+), and warm-white emissions (Bi3+/Te4+), respectively. The broad efficient dual emission in Bi3+/Te4+ co-doped Cs2HfCl6 is assigned to the typical 3P1 → 1S0 transition emission from Bi3+ originating from [BiHf + VCl] and self-trapped excitons (STEs) from Te4+. Moreover, the concentration-optimized Cs2HfCl6:Te4+ shows excellent antiwater stability and high photoluminescence quantum yield (PLQY) of ∼70%. Meanwhile, a white light-emitting diode (WLED) fabricated using Bi3+/Te4+ co-doped Cs2HfCl6 is close to warm white with a color rendering index (CRI) of 75.4, CIE color coordinate of (0.370, 0.393), and a correlated color temperature (CCT) of 4380 K. These results suggest that Bi3+/Te4+ co-doped all-inorganic lead-free Cs2HfCl6 is a potential single-phase white light-emitting phosphor candidate for solid-state lightings.

Highly efficient Fe3+-doped A2BB'O6 (A = Sr2+, Ca2+; B, B' = In3+, Sb5+, Sn4+) broadband near-infrared-emitting phosphors for spectroscopic analysis.

Near-infrared (NIR)-emitting phosphor-converted light-emitting diodes have attracted widespread attention in various applications based on NIR spectroscopy. Except for typical Cr3+-activated NIR-emitting phosphors, next-generation Cr3+-free NIR-emitting phosphors with high efficiency and tunable optical properties are highly desired to enrich the types of NIR luminescent materials for different application fields. Here, we report the Fe3+-activated Sr2-yCay(InSb)1-zSn2zO6 phosphors that exhibit unprecedented long-wavelength NIR emission. The overall emission tuning from 885 to 1005 nm with broadened full-width at half maximum from 108 to 146 nm was realized through a crystallographic site engineering strategy. The NIR emission was significantly enhanced after complete Ca2+ incorporation owing to the substitution-induced lower symmetry of the Fe3+ sites. The Ca2InSbO6:Fe3+ phosphor peaking at 935 nm showed an ultra-high internal quantum efficiency of 87%. The as-synthesized emission-tunable phosphors demonstrated great potential for NIR spectroscopy detection. This work initiates the development of efficient Fe3+-activated broadband NIR-emitting phosphors and opens up a new avenue for designing NIR-emitting phosphor materials.

Photoluminescence Properties of AScSi2O6:Cr3+ (A = Na and Li) Phosphors with High Efficiency and Thermal Stability for Near-Infrared Phosphor-Converted Light-Emitting Diode Light Sources.

Near-infrared (NIR) phosphors are fascinating photoluminescence materials with applications in phosphor-converted light-emitting diodes (pc-LEDs) for night vision lighting, which are still restricted by low efficiency and thermal stability in the current research stage. In this work, AScSi2O6 (A = Na/Li) are chosen as hosts due to a larger band gap and a single octahedral site for Cr3+ doping. The NIR-emitting Cr3+-activated AScSi2O6:Cr3+ phosphors were successfully prepared by a common high-temperature solid-state method. X-ray diffraction and Rietveld refinement confirm that the Cr3+ prefers to enter the Sc3+-octahedral lattice site in the AScSi2O6 structure. Under blue light excitation, AScSi2O6:Cr3+ phosphors exhibit broadband NIR emission from 700 to 1100 nm with a full width at half-maximum of ∼150 nm owing to the 4T2 → 4A2 electron transition of Cr3+. The photoluminescence properties were enhanced by adjusting the fluxes and sintering conditions, and highly efficient LiScSi2O6:Cr3+ NIR phosphors with external quantum efficiencies of 33.4% were obtained. Moreover, the optimized LiScSi2O6:Cr3+ exhibits excellent thermal stability (75% at 150 °C) with an activation energy of 0.33 eV. Importantly, the fabricated NIR pc-LED with the highly efficient LiScSi2O6:Cr3+ phosphor demonstrates brighter NIR light and a higher luminous efficacy than the NaScSi2O6:Cr3+ phosphor in night vision.

Regulation of Local Site Structures to Stabilize Mixed-Valence Eu2+/3+ under a Reducing Atmosphere for Multicolor Photoluminescence.

Co-doping mixed-valence Eu2+/3+ in a single-phase phosphor is an efficient method to realize the emission color regulation, which holds great potential for anticounterfeiting and ratiometric temperature sensing. Here, the mixed-valence Eu-doped Sr1.95+xLi1-xSi1-xAlxO4F (0 ≤ x ≤ 0.25) phosphors were designed and prepared under a reducing atmosphere. The correlation of local phase structures and luminescence properties was discussed. Replacing Si4+-Li+ ion pairs with Al3+-Sr2+ ion pairs compresses the Sr sites occupied by Eu2+, and it stabilizes Eu3+ in a reducing atmosphere and leads to the coexistence of Eu2+ and Eu3+ in single-phase Sr1.95+xLi1-xSi1-xAlxO4F:0.05Eu (0 ≤ x ≤ 0.25) phosphors. Based on the wavelength-dependent luminescence color behaviors of Sr1.95+xLi1-xSi1-xAlxO4F:0.05Eu phosphors, the fluorescent anticounterfeit papers/patterns containing Sr1.95+xLi1-xSi1-xAlxO4F:0.05Eu phosphors were the same as ordinary paper under ambient conditions. However, the hidden colors or images can be read out with green-orange luminescence under 365/300 nm light excitation. Benefiting from the diverse thermal response emission behaviors of Eu2+ (530 nm) and Eu3+ (703 nm), Sr1.95+xLi1-xSi1-xAlxO4F:0.05Eu phosphors exhibit temperature sensing performances, with the maximum absolute and relative sensitivity being 0.0294 K-1 at 573 K and 0.83% K-1 at 348 K. More importantly, Sr1.95+xLi1-xSi1-xAlxO4F:0.05Eu phosphors showed excellent stability in humid, acid, and alkali environments, which contributed to applying mixed-valence Eu2+/3+-doped Sr1.95+xLi1-xSi1-xAlxO4F to the fields of multicolor anticounterfeiting and noncontact optical thermometry.

Core-Shell Structured Upconversion/Lead-Free Perovskite Nanoparticles for Anticounterfeiting Applications.

In view of their excellent luminescence properties, nanocrystalline metal halide perovskites have diverse optoelectronic applications, including those related to anticounterfeiting. However, high-quality optical anticounterfeiting typically requires multiple encryptions relying on several optical modes to ensure information security. Herein, an efficient anticounterfeiting strategy based on dual optical encryption is realized by combining up- and downconversion luminescence in a nanocomposite with NaYF4 : Er3+ ,Yb3+ as core and a CsMnCl3 as shell. The emission color of this nanocomposite depends on the penetration depth of incident radiation and can be changed by varying the excitation source (980 nm laser or UV light) to produce different luminescent patterns. This feature allows one to effectively improve the anticounterfeiting index and fabricate professional anticounterfeiting materials.

Encapsulation of lead halide perovskite quantum dots in mesoporous NaYF4 matrices with enhanced stability for anti-counterfeiting.

All-inorganic cesium lead halide (CsPbX3, X = Cl, Br, and I) perovskite quantum dots (PQDs) have great potential application due to their unique optoelectronic properties. However, poor luminescence stability caused by some inevitable factors such as light, moisture and heat always restricts their practical application. In this work, the stability of CsPbX3 (X = Cl0.5Br0.5, Br, and Br0.5I0.5) PQDs is improved by encapsulating them in stable hollow mesoporous NaYF4:Yb,Tm nanoparticles (HMNPs). Compared to pristine PQDs, HMNP-PQD composites exhibit stable photoluminescence properties that can be maintained for more than 60 days under ambient atmospheric conditions. Thanks to the protection of HMNPs, the composites show much higher long-term stability in highly humid air and enhanced stability against UV light treatment compared to naked CsPbBr3 PQDs. Based on the proposed confinement effects of PQDs coordinated with the hollow mesoporous structure of NaYF4:Yb/Tm, the related structural model of NaYF4:Yb/Tm@PQD composites is discussed. Moreover, dual-mode luminescence can be observed in the NaYF4:Yb/Tm@PQD nanocomposites under 365 nm UV light and 980 nm laser excitation, indicating that the as-designed composites have great potential for dual-mode anti-counterfeiting application. This work provides a new idea for the stabilization and application of CsPbX3 PQDs.

NIR-Triggered Multi-Mode Antitumor Therapy Based on Bi2 Se3 /Au Heterostructure with Enhanced Efficacy.

Of all the reaction oxygen species (ROS) therapeutic strategies, NIR light-induced photocatalytic therapy (PCT) based on semiconductor nanomaterials has attracted increasing attention. However, the photocatalysts suffer from rapid recombination of electron-hole pairs due to the narrow band gaps, which are greatly restricted in PCT application. Herein, Bi2 Se3 /Au heterostructured photocatalysts are fabricated to solve the problems by introducing Au nanoparticles (NPs) in situ on the surface of the hollow mesoporous structured Bi2 Se3 . Owing to the lower work function of Au NPs, the photo-induced electrons are easier to transfer and assemble on their surfaces, resulting in the increased separation of the electron-hole pairs with efficient ROS generation. Besides, Bi2 Se3 /Au heterostructures also enhance the photothermal efficiency due to the effective orbital overlaps with accelerated electron migrations according to density functional theory calculations. Moreover, the PLGA-PEG and the doxorubicin (DOX) are introduced for photothermal-triggered drug release in the system. The Bi2 Se3 /Au heterostructures also displays excellent infrared thermal (IRT) and computed tomography (CT) dual-modal imaging property for promising cancer diagnosis. Collectively, Bi2 Se3 /Au@PLGA-PEG-DOX exhibits prominent tumor inhibition effect based on synchronous PTT, PCT and chemotherapy triggered by NIR light for efficient antitumor treatment.

Simultaneous Broadening and Enhancement of Cr3+ Photoluminescence in LiIn2 SbO6 by Chemical Unit Cosubstitution: Night-Vision and Near-Infrared Spectroscopy Detection Applications.

Near-infrared (NIR)-emitting phosphor materials have been extensively developed for optoelectronic and biomedical applications. Although Cr3+ -activated phosphors have been widely reported, it is challenging to achieve ultra-broad and tunable NIR emission. Here, a new ultra-broadband NIR-emitting LiIn2 SbO6 :Cr3+ phosphor with emission peak at 965 nm and a full-width at half maximum of 217 nm is reported. Controllable emission tuning from 965 to 892 nm is achieved by chemical unit cosubstitution of [Zn2+ -Zn2+ ] for [Li+ -In3+ ], which can be ascribed to the upshift of 4 T2g energy level due to the strengthened crystal field. Moreover, the emission is greatly enhanced, and the FWHM reaches 235 nm. The as-prepared luminescent tunable NIR-emitting phosphors have demonstrated the potential in night-vision and NIR spectroscopy techniques. This work proves the feasibility of chemical unit cosubstitution strategy in emission tuning of Cr3+ -doped phosphors, which can stimulate further studies on the emission-tunable NIR-emitting phosphor materials.

Thermally stable and highly efficient red-emitting Eu3+-doped Cs3GdGe3O9 phosphors for WLEDs: non-concentration quenching and negative thermal expansion.

Red phosphor materials play a key role in improving the lighting and backlit display quality of phosphor-converted white light-emitting diodes (pc-WLEDs). However, the development of a red phosphor with simultaneous high efficiency, excellent thermal stability and high colour purity is still a challenge. In this work, unique non-concentration quenching in solid-solution Cs3Gd1 - xGe3O9:xEu3+ (CGGO:xEu3+) (x = 0.1-1.0) phosphors is successfully developed to achieve a highly efficient red-emitting Cs3EuGe3O9 (CEGO) phosphor. Under the optimal 464 nm blue light excitation, CEGO shows a strong red emission at 611 nm with a high colour purity of 95.07% and a high internal quantum efficiency of 94%. Impressively, this red-emitting CEGO phosphor exhibits a better thermal stability at higher temperatures (175-250 °C, >90%) than typical red K2SiF6:Mn4+ and Y2O3:Eu3+ phosphors, and has a remarkable volumetric negative thermal expansion (coefficient of thermal expansion, α = -5.06 × 10-5/°C, 25-250 °C). By employing this red CEGO phosphor, a fabricated pc-WLED emits warm white light with colour coordinates (0.364, 0.383), a high colour rendering index (CRI = 89.7), and a low colour coordinate temperature (CCT = 4508 K). These results indicate that this highly efficient red-emitting phosphor has great potential as a red component for pc-WLEDs, opening a new perspective for developing new phosphor materials.

Solvatochromic Photoluminescent Effects in All-Inorganic Manganese(II)-Based Perovskites by Highly Selective Solvent-Induced Crystal-to-Crystal Phase Transformations.

The development of lead-free perovskite photoelectric materials has been an extensive focus in the recent years. Herein, a novel one-dimensional (1D) lead-free CsMnCl3 (H2 O)2 single crystal is reported with solvatochromic photoluminescence properties. Interestingly, after contact with N,N-dimethylacetamide (DMAC) or N,N-dimethylformamide (DMF), the crystal structure can transform from 1D CsMnCl3 (H2 O)2 to 0D Cs3 MnCl5 and finally transform into 0D Cs2 MnCl4 (H2 O)2 . The solvent-induced crystal-to-crystal phase transformations are accompanied by loss and regaining of water of crystallization, leading to the change of the coordination number of Mn2+ . Correspondingly, the luminescence changes from red to bright green and finally back to red emission. By fabricating a test-paper containing CsMnCl3 (H2 O)2 , DMAC and DMF can be detected quickly with a response time of less than one minute. These results can expand potential applications for low-dimensional lead-free perovskites.

Facile solution synthesis of Bi3+/Yb3+ ions co-doped Cs2Na0.6Ag0.4InCl6 double perovskites with near-infrared emission.

Double perovskites have attracted wide attention due to their low toxicity and good thermal stability. Doping with active elements is a promising method to endow perovskites with excellent optical, electrical or magnetic properties. Herein, a facile aqueous solution method is developed to synthesize Bi3+-Yb3+ co-doped Cs2Na0.6Ag0.4InCl6 double perovskite. Besides the intrinsic warm white self-trapped exciton (STE) emission that originated from the Cs2Na0.6Ag0.4InCl6 host, the samples also exhibit a strong near-infrared emission assigned to the 2F5/2 → 2F7/2 transition of octahedral coordinated Yb3+ ions upon excitation with ultraviolet light. The optimized sample shows a markedly high photoluminescence quantum yield of 84.7%. The photophysical studies such as photoluminescence (PL) and photoluminescence excitation spectra, temperature-dependent PL spectra, and PL decay curves reveal that the strong Yb3+ emission is attributed to the energy transfer from STEs to the Yb3+ ions. Finally, the lead-free double perovskite phosphor-converted LED containing visible and NIR regions was fabricated, with 8.92 mW output power at 100 mA drive current. The results show the great potential of the as-prepared crystals in optoelectronics applications.

Broadband Near-Infrared Emitting Ca2LuScGa2Ge2O12:Cr3+ Phosphors: Luminescence Properties and Application in Light-Emitting Diodes.

In recent years, the demand for near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) has increased rapidly, leading to more and more attention being paid to the research of broad-band near-infrared phosphors. In this work, Cr3+-doped Ca2LuScGa2Ge2O12 (CLSGG:Cr3+) phosphors with broad-band NIR emission were prepared through traditional high-temperature solid-state reactions. The crystal structures of the phosphors were analyzed by X-ray diffraction (XRD) and Rietveld refinement. The photoluminescence excitation (PLE) spectra of the synthesized CLSGG:Cr3+ phosphors exhibit a strong absorption band in the 400-500 nm region, which matches well with a blue-light-emitting chip. The photoluminescence (PL) spectra of the phosphors show broad-band emission ranging from 650 to 1100 nm with a full width at half-maximum (fwhm) of about 150 nm. At 423 K, the integrated emission intensity of CLSGG:0.02Cr3+ is about 59% of that at room temperature. A NIR pc-LED device was fabricated by combining a mixture of as-synthesized CLSGG:0.02Cr3+ phosphor and silicone with a 460 nm blue-light-emitting chip. Under a driving current of 100 mA, the output power of the device can achieve 1.213 mW, indicating that the as-prepared phosphors are promising for NIR pc-LED applications.

Highly Efficient Cyan-Green Emission in Self-Activated Rb3RV2O8 (R = Y, Lu) Vanadate Phosphors for Full-Spectrum White Light-Emitting Diodes (LEDs).

Phosphor-converted white-light-emitting diodes (pc-WLEDs) rely on combining a near-ultraviolet (n-UV) or blue chip with trichromatic and yellow-emitting phosphors. It is challenging to discover cyan-green-emitting (480-520 nm) phosphors for compensating the spectral gap and producing full-spectrum white light. In this work, we successfully discovered two unprecedented bright cyan-green emitting Rb3RV2O8 (R = Y, Lu) phosphors that gives emission bands centered at 500 nm upon 362 nm n-UV light excitation. Interestingly, the both self-activated compounds exhibit high internal quantum efficiencies (IQEs) of 71% for Rb3YV2O8 and 85% for Rb3LuV2O8, respectively. Moreover, controllable emission color can be successfully tuned from cyan-green to orange-red across the warm white light region by design strategy of VO43- → Eu3+ energy transfer. The thermal quenching of as-prepared phosphors could be effectively mitigated by this design strategy. Finally, the as-fabricated n-UV (λex = 370 nm) pumped phosphor-converted (pc) W-LED devices utilizing Rb3RV2O8 (R = Y, Lu) along with commercial phosphors demonstrate well-distributed warm white light with high color-rendering index (CRI) of 91.9 and 93.5, and a low correlated color temperature (CCT) of 5095 and 4946 K. It suggests that the both vanadate phosphors have potential applications in full-spectrum pc-WLEDs.

Strategies for Designing Antithermal-Quenching Red Phosphors.

Nowadays, red phosphor plays a key role in improving the lighting quality and color rendering index of phosphor-converted white light emitting diodes (w-LEDs). However, the development of thermally stable and highly efficient red phosphor is still a pivotal challenge. Herein, a new strategy to design antithermal-quenching red emission in Eu3+, Mn4+-codoped phosphors is proposed. The photoluminescence intensity of Mg3Y2(1- y )Ge3O12:yEu3+, Mn4+ (0 ≤ y ≤ 1) phosphors continuously enhances with rising temperature from 298 to 523 K based on Eu3+ → Mn4+ energy transfer. For Mg3Eu2Ge3O12:Mn4+ sample, the integrated intensity at 523 K remarkably reaches 120% of that at 298 K. Interestingly, through codoping Eu3+ and Mn4+ in Mg3Y2Ge3O12, the photoluminescence color is controllably tuned from orangish-red (610 nm) to deep-red (660 nm) light by changing Eu3+ concentration. The fabricated w-LEDs exhibit superior warm white light with low corrected color temperature (CCT = 4848 K) and high color rendering index (R a = 96.2), indicating the promising red component for w-LED applications. Based on the abnormal increase in antistokes peaks of Mn4+ with temperatures, Mg3Eu2Ge3O12:Mn4+ phosphor also presents a potential application in optical thermometry sensors. This work initiates a new insight to construct thermally stable and spectra-tunable red phosphors for various optical applications.

Cu2 MoS4 /Au Heterostructures with Enhanced Catalase-Like Activity and Photoconversion Efficiency for Primary/Metastatic Tumors Eradication by Phototherapy-Induced Immunotherapy.

Photoimmunotherapy can not only effectively ablate the primary tumor but also trigger strong antitumor immune responses against metastatic tumors by inducing immunogenic cell death. Herein, Cu2 MoS4 (CMS)/Au heterostructures are constructed by depositing plasmonic Au nanoparticles onto CMS nanosheets, which exhibit enhanced absorption in near-infrared (NIR) region due to the newly formed mid-gap state across the Fermi level based on the hybridization between Au 5d orbitals and S 3p orbitals, thus resulting in more excellent photothermal therapy and photodynamic therapy (PDT) effect than single CMS upon NIR laser irradiation. The CMS and CMS/Au can also serve as catalase to effectively relieve tumor hypoxia, which can enhance the therapeutic effect of O2 -dependent PDT. Notably, the NIR laser-irradiated CMS/Au can elicit strong immune responses via promoting dendritic cells maturation, cytokine secretion, and activating antitumor effector T-cell responses for both primary and metastatic tumors eradication. Moreover, CMS/Au exhibits outstanding photoacoustic and computed tomography imaging performance owing to its excellent photothermal conversion and X-ray attenuation ability. Overall, the work provides an imaging-guided and phototherapy-induced immunotherapy based on constructing CMS/Au heterostructures for effectively tumor ablation and cancer metastasis inhibition.