Simultaneous co-substitution of Sr2+/Fe3+ in hydroxyapatite nanoparticles for potential biomedical applications

In human, strontium (Sr) follows the same physiological pathway as calcium and thus could be used for improving the bioactivity and osteoconductivity of hydroxyapatite (HAp) in bone tissues. Similarly, iron (Fe) can potentially play an important role in bone remodeling due to its magnetic properties. Therefore, the current study was aimed to simultaneously co-substitute Sr²⁺/Fe³⁺ in HAp nanoparticles for various potential biomedical applications. The Sr²⁺/Fe³⁺ co-substituted HAp nanoparticles were systematically synthesized through sonication-assisted aqueous precipitation method. The as-synthesized nanoparticles were evaluated for different physicochemical and biological properties. X-ray diffraction (XRD) patterns of Sr²⁺/Fe³⁺ co-substituted HAp nanoparticles confirmed their phase purity and showed hexagonal-like structure. Scanning electron microscope (SEM) micrographs showed an agglomerated rod-like morphology of HAp nanoparticles which contained pores consisted of small spheroids. The nanoparticles displayed magnetization (Ms) reliance on the loading level of mole % (X?=?Fe³⁺) and exhibited tunable porosity and microhardness (Hv) upon heat treatment. The nanoparticles showed less than 5% hemolysis demonstrating high blood compatibility with high in vitro bioactivity performance. The multifunctional properties of synthesized nanoparticles make them a potential candidate for various biomedical applications; including bone grafting and guided bone regeneration, targeted drug delivery, magnetic resonance imaging, and hyperthermia based cancer treatment.     

Synthesis and characterisation of nanophase hydroxyapatite co-substituted with strontium and zinc

In order to develop new bioactive calcium phosphate (CaP) materials to repair bone defects, it is important to ensure these materials more closely mimic the non-stoichiometric nature of biological hydroxyapatite (HA). Typically, biological HA combines various CaP phases with different impurity ions, which substitute within the HA lattice, including strontium (Sr²⁺), zinc (Zn²⁺), magnesium (Mg²⁺), carbonate (CO₃^2-) and fluoride (F^-), but to name a few. In addition to this biological HA have dimensions in the nanometre (nm) range, usually 60?nm in length by 5–20?nm wide. Both the effects of ion substitution and the nano-size crystals are seen as important factors for enhancing their potential biofunctionality. The driving hypothesis was to successfully synthesise nanoscale hydroxyapatite (nHA), co-substituted with strontium (Sr²⁺) and zinc (Zn²⁺) ions in varying concentrations using an aqueous precipitation method and to understand their chemical and physical properties. The materials were characterised using Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM) techniques. The FTIR, XRD and XPS results confirmed that the nHA was successfully co-substituted with Sr²⁺ and Zn²⁺, replacing Ca²⁺ within the nHA lattice at varying concentrations. The FTIR results confirmed that all of the samples were carbonated, with a significant loss of hydroxylation as a consequence of the incorporation of Sr²⁺ and Zn²⁺ into the nHA lattice. The TEM results showed that each sample produced was nano-sized, with the Sr/Zn-10%nHA having the smallest sized crystals approximately 17.6 ± 3.3?nm long and 10.2 ± 1.4?nm wide. None of the materials synthesised here in this study contained any other impurity CaP phases. Therefore, this study has shown that co-substituted nHA can be prepared, and that the degree of substitution (and the substituting ion) can have a profound effect on the attendant materials’ properties.     

Strontium and zinc co-substituted nanophase hydroxyapatite

It is well documented that biological hydroxyapatite (HA) differs from pure and synthetically produced HA, and contains of a mixture of calcium phosphate (CaP) phases in addition to a range of impurity ions, such as strontium (Sr²⁺), zinc (Zn²⁺), magnesium (Mg²⁺), fluoride (F^-) and carbonate(CO₃^2-), but to name a few. Further to this, biological apatite is generally in the form of rod (or needle-like) crystals in the nanometre (nm) size range, typically 60 nm in length by 5–20 nm wide. In this study, a range of nano-hydroxyapatite (nHA), substituted nHA materials and co-substituted nHA (based on Sr²⁺ and Zn²⁺) were manufactured using an aqueous precipitation method. Sr²⁺ and Zn²⁺ were chosen due to the significant performance enhancements that these substitutions can deliver. The materials were then characterised using Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM) techniques. The TEM results show that all of the samples produced were nano-sized, with Zn-substituted nHA being the smallest crystals around 27 nm long and 8 nm wide. The FTIR, XRD and XPS results all confirm that the materials had undergone substitution with either Sr²⁺ and Zn²⁺, for Ca²⁺ within the HA lattice (or both in the case of the co-substituted materials). The FTIR results confirmed that all of the samples were carbonated, with a significant loss of hydroxylation as a consequence of the incorporation of Sr²⁺ and Zn²⁺ into the HA lattice. None of the materials synthesised here in this study contained any other impurity CaP phases. Therefore this study has shown that substituted and co-substituted nanoscale apatites can be prepared, and that the degree of substitution (and the substituting ion) can have a profound effect of the attendant materials’ properties.     

Synthesis,Characterization, Antibacterial Properties,and In Vitro Studies of Selenium and Strontium Co-Substituted Hydroxyapatite

In this study, as a measure to enhance the antimicrobial activity of biomaterials, the selenium ions have been substituted into hydroxyapatite (HA) at different concentration levels. To balance the potential cytotoxic effects of selenite ions (SeO₃²⁻) in HA, strontium (Sr²⁺) was co-substituted at the same concentration. Selenium and strontium-substituted hydroxyapatites (Se-Sr-HA) at equal molar ratios of x Se/(Se + P) and x Sr/(Sr + Ca) at (x = 0, 0.01, 0.03, 0.05, 0.1, and 0.2) were synthesized via the wet precipitation route and sintered at 900 °C. The effect of the two-ion concentration on morphology, surface charge, composition, antibacterial ability, and cell viability were studied. X-ray diffraction verified the phase purity and confirmed the substitution of selenium and strontium ions. Acellular in vitro bioactivity tests revealed that Se-Sr-HA was highly bioactive compared to pure HA. Se-Sr-HA samples showed excellent antibacterial activity against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus carnosus) bacterial strains. In vitro cell–material interaction, using human osteosarcoma cells MG-63 studied by WST-8 assay, showed that Se-HA has a cytotoxic effect; however, the co-substitution of strontium in Se-HA offsets the negative impact of selenium and enhanced the biological properties of HA. Hence, the prepared samples are a suitable choice for antibacterial coatings and bone filler applications.     

Local coordination,electronic structure,and thermal quenching of Ce3+ in isostructural Sr2GdAlO5 and Sr3AlO4F phosphors

Sr₂GdAlO₅:Ce and Sr₃AlO₄F:Ce are isostructural phosphors in which the Ce³⁺ 4f-5d₁ transition can be efficiently excited by a photon with energy lower than 3.1 eV. Herein, we analyze the crystal chemistry of the Ce³⁺ local coordination, compare the thermal quenching behavior and construct the electronic structure of Ce³⁺ in them. The Rietveld refinement on two occupancy models suggests that Gd³⁺ only occupies the 8h site in Sr₂GdAlO₅; this provides a hint on the preferred occupancy of dopant Ce³⁺ in this site. The large crystal filed splitting of Ce_8h is mainly due to the fact that the 8h site is bonded to two oxygen with relatively short d_Sr/Gd-O and forms a quasi-square antiprism which experiences a large distortion. The Ce³⁺ 5d-4f luminescence in Sr₃AlO₄F is much more stable against thermal quenching than that in Sr₂GdAlO₅, as evidenced by the temperature-dependent luminescence intensity and luminescence decay studies. The energy of the O²⁻-Eu^3+/2+ and O²⁻-Ce^4+/3+ charge transfer as well as bandgap were estimated and the electronic structure of Ce³⁺ were constructed. A larger energy barrier ΔE_dC between the Ce³⁺ 5d₁ level and the conduction band bottom in Sr₃AlO₄F is seen from the Vacuum Referred Binding Energy (VRBE) diagrams which explains the higher thermal quenching temperature by thermal ionization model.     

Synthesis and photoluminescence properties of Eu2+/Eu3+ or Ce3+/Eu3+ co-doped Sr5(BO3)3F compounds

The synthesis and photo-luminescence properties of Eu²⁺/Eu³⁺ or Ce³⁺/Eu³⁺ co-doped Sr₅(BO₃)₃F compounds are reported. Using the Sr₅(BO₃)₃F as the host, through the solid state reaction under the reductive atmosphere, Eu²⁺/Eu³⁺ and Ce³⁺/Eu³⁺co-doped samples were prepared. These compounds exhibit good photo-luminescence properties. Under the excitation of 376 nm, an unusual red orange emission coming from the Eu²⁺ ions can be obtained in Eu ions doped Sr₅(BO₃)₃F, which exhibits a broadband emission in the range of 450–800 nm with the peak at around 600 nm. At the same time, the characteristic f-f excitation and emission of Eu³⁺ can improve and adjust the Eu²⁺ emission in Eu³⁺/Eu²⁺ codoped Sr₅(BO₃)₃F. In addition, the adjustable luminescence properties from blue to white of Sr₅(BO₃)₃F:Ce³⁺, Eu³⁺ are investigated. The energy transfer behavior from Ce³⁺ to Eu³⁺ was confirmed. In the spectra of the co-doped samples, we can hardly observe the characteristic peak of Eu²⁺, because Ce⁴⁺ can oxidize Eu²⁺ to Eu³⁺, and Ce⁴⁺ itself is reduced to Ce³⁺. The CIE coordinates from (0.2758, 0.2420) to (0.3857, 0.3015) show Sr₅(BO₃)₃F:3%Ce³⁺, x%Eu³⁺ (x = 1,3,5,7,9) are in the white light emission region. All results demonstrate that the Sr₅(BO₃)₃F:Eu³⁺/Eu²⁺ and Sr₅(BO₃)₃F:Ce³⁺/Eu³⁺ phosphors have good application prospects for LED plant growth and white LED, respectively. The bond energy method was used to explain the reason why the Eu²⁺/Eu³⁺ ion instead of only Eu²⁺ and Ce³⁺/Eu³⁺ instead of Ce³⁺/Eu³⁺/Eu²⁺ can exist in the host Sr₅(BO₃)₃F. The theoretical analysis agree well with the experimental result.     

Partial cation substitution of tunable blue-cyan-emitting Ba2B2O5:Ce3+ for near-UV white LEDs

In this study, Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ ions act to tune the emission band to the blue-cyan region in Ba_xSr_yB₂O₅:Ce³⁺ (BSBO), Ba_xCa_zB₂O₅:Ce³⁺ (BCBO), Ba_xZn_uB₂O₅:Ce³⁺ (BZBO), and Ba_xMg_vB₂O₅:Ce³⁺ (BMBO) phosphors. A red shift occurs with the increase of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ concentration, and a blue shift occurs when the concentrations of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ exceed the critical value. The emission color can be tuned from deep blue (0.15, 0.12) to cyan (0.16, 0.27) upon 365 nm UV lamp excitation due to the crystal field splitting and centroid shifts. The excitation band shift to long wavelength by introducing ions, so that the synthesized phosphor can be better matched with the n-UV chip. The emission intensity slowly decreases with the temperature increasing. Therefore, the BMBO:Ce³⁺, BZBO:Ce³⁺, BCBO:Ce³⁺, and BSBO:Ce³⁺ phosphors with relatively good thermal stability were synthesized, which could have potential applications in the n-UV white LEDs.     

Luminescence properties and energy transfer investigations of Sr2B2O5:Ce3+,Tb3+ phosphors

Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were synthesized by the solid-state method. X-ray diffraction (XRD) was used to characterize the phase structure. The luminescent properties of Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were investigated by using the photoluminescence emission, excitation spectra and reflectance spectra, respectively. The excitation spectra indicate that this phosphor can be effectively excited by near ultraviolet (n-UV) light of 317 nm. Under the excitation of 317 nm, Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors exhibited blue emission corresponding to the f–d transition of Ce³⁺ ions and green emission bands corresponding to the f–f transition of Tb³⁺ ions, respectively. The Reflectance spectra of the Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors are noted that combine with Ce³⁺ and Tb³⁺ ion absorptions. Effective energy transfer occurred from Ce³⁺ to Tb³⁺ in Sr₂B₂O₅ host due to the observed spectra overlap between the emission spectrum of Ce³⁺ ion and the excitation spectrum of Tb³⁺ ion. The energy transfer efficiency from Ce³⁺ ion to Tb³⁺ ion was also calculated to be 90%. The phosphor Sr₂B₂O₅:Ce³⁺,Tb³⁺ could be considered as one of double emission phosphor for n-UV excited white light emitting diodes.     

Morphology Tunable Self‐Assembled Sr2P2O7:Ce3+, Mn2+ Phosphor and Luminescence Properties

Uniform orange‐to‐red spherical phosphors of Sr₂P₂O₇:Ce³⁺, Mn²⁺ have been synthesized by the co‐precipitation method and characterized by X‐ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. The results indicate that the morphology, size, and photoluminescence properties of Sr₂P₂O₇:Ce³⁺, Mn²⁺ phosphors can be effectively controlled by the reaction and the sintering temperatures. Energy transfer from Ce³⁺ to Mn²⁺ in Sr₂P₂O₇ phosphor was observed from photoluminescence spectra of Sr₂P₂O₇:Ce³⁺, Sr₂P₂O₇:Mn²⁺, and Sr₂P₂O₇:Ce³⁺, Mn²⁺. Moreover, based on a self‐assembly process, a possible formation mechanism for the spherical phosphors is proposed. The uniform phosphor spheres obtained in this work exhibit great potential for high‐resolution display devices such as light emitting diodes.     

Strontium and copper co-substituted hydroxyapatite-based coatings with improved antibacterial activity and cytocompatibility fabricated by electrodeposition

Bacterial infection are serious complications for biomedical implants in the orthopedic and dental fields, and the ideal implants should combine good antibacterial ability and bioactivity. In this paper, we have fabricated the strontium/copper substituted hydroxyapatite (SrCuHA) coating on the commercially pure titanium (CP-Ti) and studied their effect on antibacterial and in vitro cytocompatible properties. Cu was incorporated into HA in order to improve its antimicrobial properties. Sr was added as a second binary element to improve the biocompatibility. The structural and morphological characteristics of the SrCuHA coatings were investigated using various analytical techniques. The presence of Sr²⁺ and Cu²⁺ in solution led to reduced roughness of the coating and finer nucleus size formed. The results highlight that Sr²⁺ and Cu²⁺ were homogenously incorporated into HA lattice to form SrCuHA coatings. Inductively coupled plasma mass spectrometry (ICP-MS) was used for the leach out analysis of the samples. A low contact angle value revealed the hydrophilic nature. In vitro electrochemical corrosion studies indicated that the SrCuHA coating sustain in the stimulated body-fluid (SBF), exhibiting superior corrosion resistance with a lower corrosion penetration rate than the bare CP-Ti substrate. The SrCuHA coatings can kill Escherichia coli to a certain extent during the first few days, which might be due to the Cu substitution in the coating. An enhancement of in vitro osteoblast adhesion, proliferation, and alkaline phosphatase activity was observed, which could lead to the optimistic orthopedic and dental applications.     

Preparation and Application of Strong Near‐Infrared Emission Phosphor Sr3SiO5:Ce3+,Al3+,Nd3+

This work investigated the near‐infrared (NIR) emission properties of mCe³⁺, xNd³⁺ codoped Sr_3?m?x(Si_1?m?xAl_m+x)O₅ phosphors. Samples with various doping concentrations were synthesized by the high‐temperature solid‐state reaction. Al³⁺ ions have the ability to promote Ce³⁺ ions to enter into the Sr²⁺ sites and to improve the visible emission of Ce³⁺. Thus the NIR emission of Nd³⁺ is enhanced by the energy‐transfer process, which occurred from Ce³⁺ to Nd³⁺. The device based on these NIR emission phosphors is fabricated and combined with a commercial c‐Si solar cell for performance testing. Short‐circuit current density of the solar cell is increased by 7.7%. Results of this work suggest that the Sr_2.95Si_0.95Al_0.05O₅:0.025Ce³⁺, 0.025Nd³⁺ phosphors can be used as spectral convertors to improve the efficiency of c‐Si solar cell.     

Effects of Sr2+/Zn2+ co-substitution on crystal structure and properties of nano-β-tricalcium phosphate

The incorporation of therapeutic ions like Sr²⁺, Si⁴⁺, Zn²⁺ and Li⁺ into biomaterials has become a promising approach to promote bone regeneration. However, the effects of Sr²⁺ and Zn²⁺ co-substitution on the crystal structure and properties of β-tricalcium phosphate (β-TCP) have not been elucidated well. In this study, Sr²⁺/Zn²⁺ co-substituted β-tricalcium phosphate (SrZnTCP) nano-powders with different extents of substitution (0–4.8 mol%) were synthesized by poly(ethylene glycol)-assisted co-precipitation and subsequent heat treatment. The as-synthesized SrZnTCP nano-powders were characterized by x-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis, Rietveld refinement and differential scanning calorimetry. The results showed that the conversion of calcium-deficient apatite to β-TCP was achieved after heat-treatment above 800 °C. The a-axis and c-axis lattice parameters gradually decreased with increasing level of Sr²⁺/Zn²⁺ co-substitution in β-TCP lattice. Sr²⁺ and Zn²⁺ preferentially occupied the ninefold coordinated Ca (4) sites and the sixfold coordinated Ca (5) sites, respectively. The co-substitution of Sr²⁺ and Zn²⁺ for Ca²⁺ significantly improved the thermal stability of β-TCP. The release rate of Zn²⁺ from SrZnTCP depended on Ca²⁺ concentration over 63-day immersion in PBS solution while that of Sr²⁺ was not affected by Ca²⁺ concentration. The amount of Sr²⁺ released increased with increasing Sr²⁺ content in SrZnTCP. Collectively, SrZnTCP showed great promise as a Sr²⁺/Zn²⁺-releasing biomaterial for bone repair, although no obvious mineralization was observed on β-TCP and SrZnTCP disc samples during 56 days of immersion in simulated body fluid.     

Effect of codoping Ce3+ on the luminescence properties of Sr9Mg1.5(PO4)7:Eu2+ orange–yellow phosphor

Sr₉Mg_1.5(PO₄)₇:Eu²⁺ has recently been reported as a promising blue light-excited orange–yellow phosphor that can be used in white LED device. Here, Ce³⁺-codoping is found to be an effective strategy to improve the luminescence performance of Sr₉Mg_1.5(PO₄)₇:Eu²⁺ phosphor. The coexistence of Eu²⁺ and Eu³⁺ ions has been verified via photoluminescence spectral analysis. The reduction of Eu³⁺ to Eu²⁺ in Sr₉Mg_1.5(PO₄)₇ lattice cannot be completed in a reducing atmosphere, but can be promoted through codoping with Ce³⁺ ions to a great extent, which finally increase the effective concentration of Eu²⁺ in the crystal lattice. The Eu³⁺−Eu²⁺ reduction mechanism is analyzed using a charge compensation model. This work not only achieves enhanced luminescence of the Sr₉Mg_1.5(PO₄)₇:Eu²⁺ phosphor by codoping with Ce³⁺ ions, but also provides new insights into the design of Ce³⁺/Eu²⁺ codoped luminescent materials.     

Decay Behavior in Ce3+‐doped La3Si6N11 and Lu3Al5O12 Phosphors

Ce³⁺‐activated light emitting diode (LED) phosphors have been extensively examined for photoluminescence, and have been the focus of many detailed structural studies. However, reports of the decay curves of Ce³⁺‐activated LED phosphors are rare. Although we have reported the decay behaviors of several Eu²⁺‐activated LED phosphors such as Sr₂SiO₄, Sr₂Si₅N₈, and CaAlSiN₃, we have never conducted an in‐depth study into the decay behavior for Ce³⁺‐activated LED phosphors. For this study, we investigated the decay curves of well‐known Ce³⁺‐activated LED phosphors such as La₃Si₆N₁₁ and Lu₃Al₅O₁₂. Similar to Eu²⁺‐activated LED phosphors, the decay behavior of Ce³⁺‐activated LED phosphors was sensitive to the Ce³⁺ concentration and to the detection wavelength. There was active nonradiative energy transfer between the Ce³⁺ activators located at different sites.     

Photoluminescence properties and energy transfer between activators at different crystallographic sites in Ce3+ doped Sr2MgAl22O36

In this paper, a series of Ce3+ doped Sr₂MgAl₂₂O₃₆ (SMA) phosphors have been prepared by high temperature solid-state reaction method. The phase structure of prepared samples was checked by the powder X-ray diffraction (XRD). The morphology of the samples was inspected using a field-emission scanning electron microscope (SEM). Under different UV radiation, this phosphor exhibits different emission bands due to the Ce³⁺ ions located at different lattice sites. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. The phosphor exhibits different concentration quenching mechanisms because the Ce³⁺ ions substitute two different crystallographic sites in the host. Moreover, the temperature dependent emission properties of SMA:Ce³⁺ were conducted from 30 °C to 200 °C, as much as 72.96% of the room-temperature emission intensity is retained at 150 °C. The SMA:Ce³⁺ phosphor exhibits bright blue emission with CIE coordinates (x=0.16, y=0.12) under UV excitation. The results indicate that SMA:Ce³⁺ phosphor has great potential applications in UV-pumped light emitting diodes.     

Antimicrobial properties of co-doped tricalcium phosphates Ca3-2x(MˊMˊˊ)x(PO4)2 (M = Zn2+, Cu2+, Mn2+ and Sr2+)

The substituted (Ca²⁺/Cu²⁺), and co-substituted (Cu²⁺/Zn²⁺), (Cu²⁺/Sr²⁺), and (Sr²⁺/Mn²⁺) β-tricalcium phosphate (β-TCP)-based Ca_3-2x(MˊMˊˊ)_x(PO₄)₂ (M = Zn²⁺, Cu²⁺, Mn²⁺ and Sr²⁺) solid solutions have been synthesized using solid-state route. The powder X-ray diffraction study shows the formation of β-TCP-type structure as the main phase in all solid solutions. The crystal structures and chemical compositions were approved using Fourier-transform infrared (FT-IR) absorption spectra and energy-dispersive X-ray spectrometry (EDX) data, respectively. The unit cell parameters and volume of as-synthesized samples directly depend on the radius of the incorporated ions. The limits of the single-phase solid solutions were found based on the possible occupation of the crystal sites in β-TCP structure. For the divalent ions with small radii, such as Cu²⁺ or Zn²⁺, the limit composition was found as Ca_2.571Mˊ_0.429–xMˊˊ_x(PO₄)₂ for Mˊ and Mˊˊ – Cu²⁺ and Zn²⁺. The enlargement of the unit cell by incorporation of Sr²⁺ allows to extend the limit of solid solutions up to Ca_2.5Sr_0.5–xMˊ_x(PO₄)₂ for Mˊ – Cu²⁺ or Mn²⁺. The antibacterial properties were studied on 4 bacteria (S. aureus, P. aeruginosa, E. coli and E. faecalis) and 1 fungus (C. albicans). It has been showed that co-doped Ca_2.5Sr_0.25Cu_0.25(PO₄)₂ sample exhibits the highest antimicrobial activity resulting in 92%, 96% and 96% inhibition growth rate for S. aureus, P. aeruginosa and E. faecalis, respectively. The antimicrobial properties are strongly related to the occupation of the crystal sites in the β-TCP structure by doping ions.     

Selectivity Study of Alkaline Earth and Divalent Transition Metal Ions on [Al3+ + Na+]-Substituted Tobermorites

Abstract

The ion-exchange selectivities of [Al³⁺ + Na⁺]-substituted tobermorites with 1–20 mol% substitution of aluminum for silicon at low loadings were investigated for Mg²⁺, Sr²⁺, Ba²⁺, and Ni²⁺. The selectivity order depended on the degree of substitution, exchanging medium, and loading of metal ions, reflecting different types of ion-exchange sites in the Al³⁺-substituted tobermorites which are an interesting group of calcium aluminosilicate cation exchangers.     

Effect of Ce dopant on upconversion and temperature sensing performances in homogeneous ultrasmall Y2O3:Yb3+/Ho3+ nanoparticles through flame aerosol synthesis

Flame aerosol synthesis (FAS) is an excellent strategy for continuous, fast, and mass production of small-size upconversion nanoparticles (UCNPs), which have high potential applications in fields like biological imaging, colour display and optical temperature sensing. However, flame-made UCNPs have received less attention, and relevant studies are limited. Herein, for the first time, we successfully fabricated cerium (Ce)-doped homogeneous ultrasmall Y₂O₃:Yb³⁺/Ho³⁺ UCNPs using a liquid-fed FAS method. Ce was doped to improve the upconversion luminescence (UCL) of the Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. The overall UCL intensity was enhanced ～77.9-fold for an optimal concentration of 20 mol% Ce-doped UCNPs, compared with the UCNPs without Ce doping with a relatively homogeneous ultrasmall size of 8–10 nm. Further studies confirmed that both trivalent (Ce³⁺) and tetravalent (Ce⁴⁺) simultaneously exist in the Y₂O₃ hosts and are critical in enhancing the UCL properties. In addition, the fluorescence intensity ratio (FIR) method was used to evaluate the thermal properties of the fabricated UCNPs. Ce doping significantly improved the thermal sensitivity of Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. An excellent relative sensitivity (S_R) of 0.622% K^?1 at 598 K was obtained for flame-made UCNPs doped with 20 mol% Ce.     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

Insight into luminescent properties,energy transfer and thermal stability of NaBa4(AlB4O9)2Cl3:Ce3+, Tb3+ phosphors

A series of Ce³⁺ and Tb³⁺ singly- and co-doped NaBa₄(AlB₄O₉)₂Cl₃ (NBAC) phosphors have been synthesized via high-temperature solid state route. The crystal structure, morphology, photoluminescent properties, thermal properties and energy transfer process between Ce³⁺ and Tb³⁺ were systematically investigated. The structure refinements indicated that the phosphors based on NBAC crystallized in P42nm polar space group in monoclinic phase. The emission color could be tuned from blue (0.1595, 0.0955) to green (0.2689, 0.4334) via changing the ratio of Ce³⁺/Tb³⁺. The energy transfer mechanism of Ce³⁺/Tb³⁺ was verified to be dipole–quadrupole interaction via the examination of decay times of Ce³⁺ based on Dexter's theory. The good thermal stability showed the intensities of Ce³⁺ at 150°C were about 66.9% and 64.88% in NBAC:0.09Ce³⁺ and NBAC:0.09Ce³⁺, 0.07Tb³⁺ of that at room temperature, and the emission intensities of Tb³⁺ remained 102.41% in NBAC:0.11Tb³⁺ and 95.22% in NBAC:0.09Ce³⁺, 0.07Tb³⁺ due to the nephelauxetic shielding effect and the highly asymmetric rigid framework structure of NBAC. The maximum external quantum efficiency (EQE) of Ce³⁺ in NBAC:0.09Ce³⁺, yTb³⁺ phosphors could reach 43.38% at y = 0.13. Overall, all the results obtained suggested that NBAC:Ce³⁺, Tb³⁺ could be a promising option for n-UV pumped phosphors.