Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Selective synthesis of mesoporous and nanorod CeVO4 without template

A simple and efficient method has been established for the selective synthesis of mesoporous and nanorod CeVO4 with different precursors by sonochemical method. CeVO4 nanorod can be simply synthesized by ultrasound irradiation of Ce(NO3)(3) and NH4VO3 in aqueous solution without any surfactant or template. While mesoporous CeVO4 with high specific surface area can be prepared with Ce(NO3)(3), V2O5 and NaOH in the same way. Mesoporous CeVO4 has a specific surface area of 122 m(2) g(-1) and an average pore size of 5.2 nm; CeVO4 nanorods have a diameter of about 5 nm, and a length of 100-150 nm. The ultrasound irradiation and ammonia in the reactive solution are two key factors in the formation of such rod-like products. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and differential thermal analyses (DTA), UV/vis absorption spectroscopy and Brunauer-Emmett-Teller (BET) were applied for characterization of the as-prepared products.

Non-isothermal crystallisation kinetics of polyamide 6/mesoporous silica nanocomposites

Non-isothermal crystallisation kinetics of a polyamide 6/mesoporous silica nanocomposite (PA6-MS) has been investigated by differential scanning calorimetry (DSC) at different cooling rates. Mandelkern, Jeziorny-Ziabicki and Ozawa methods were applied to describe this crystallisation process. The analyses show that the mesoporous silica particles act as nucleating agents in the composite and that the Avrami exponent n varies from 3.0 to 4.6. The addition of mesoporous silica influenced the mechanism of nucleation and the growth of polyamide 6 (PA6) crystallites.

Mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and a catalyst in catalytic degradation of polyethylene

The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene (PE) catalytic degradation was investigated. Here, HMCM- 41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves (SAPO1 and SAPO2) were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.

Novel acidic porous clay heterostructure with highly ordered organic-inorganic hybrid structure: one-pot synthesis of mesoporous organosilica in the galleries of clay

A new class of organic-inorganic hybrid porous clay heterostructures (HPCHs) have been prepared through the surfactant-directed assembly of organosilica in the galleries of montmorillonite. The reaction involved hydrolysis and condensation of phenyltriethoxysilane and tetraethoxysilane in the presence of intragallery surfactant templates (dodecylame and cetyltrimethylammonium ion). The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), N-2 adsorption, solid-state Si-29 and C-13 NMR, and FTIR. XRD patterns indicated a regular interstratification of the clay layers for HPCHs. Depending on loading of phenyl groups, HPCHs had BET surface areas of 390-771 m(2) g(-1), pore volumes of 0.3-0.59 cm(3) g(-1), and the framework pore sizes in the supermicropore to small mesopore range (1.2-2.6 nm). HPCHs were hydrophobic and acidic.

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

Synthesis and characterization of functionalized mesoporous silica by aerosol-assisted self-assembly

An efficient, productive, and low-cost aerosol-assisted self-assembly process has been developed to produce organically modified mesoporous silica particles via a direct co-condensation of silicate species and organosilicates that contain nonhydrolyzable functional groups in the presence of templating surfactant molecules. Different surfactants including cetyltrimethylammonium bromide, nonionic surfactant Brij-56, and triblock copolymer P123 have been used as the structure-directing agents. The organosilanes used in this study include tridecafluoro-1, 1,2,2-tetrahydrooctyltriethoxysilane, methytriethoxysilane, vinyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate. X-ray diffraction and transmission electron microscopy studies indicate the formation of particles with various mesostructures. Fourier transform infrared and solid-state nuclear magnetic resonance spectra confirm the organic ligands are covalently bound to the surface of the silica framework. The porosity, pore size, and surface area of the particles were characterized using nitrogen adsorption and desorption measurements.

Low threshold amplified spontaneous emission based on coumarin 151 encapsulated in mesoporous SBA-15

Amplified spontaneous emission (ASE) characteristics of a blue dye coumarin 151 encapsulated in a highly ordered mesoporous SBA-15 were studied. The spectra narrowing was observed and found that the threshold and loss were greatly reduced, and the gain is significantly increased compared with spin-coated coumarin 151 doped poly(4-vinylphenol) film. The ASE threshold, gain, and loss, respectively, reached 0.55 mJ pulse(-1) cm(-2), 44.78 cm(-1), and 8.9 cm(-1) for the coumarin 151 encapsulated in mesoporous SBA-15 film. The optimized lasing action owes much to the effects of the better spatial confinement of the molecules in the ordered mesoporous structure of the host SBA-15.

Covalent linking of near-infrared luminescent ternary lanthanide (Er3+, Nd3+, Yb3+) complexes on functionalized mesoporous MCM-41 and SBA-15

The near-infrared (NIR) luminescent lanthanide ions, such as Er(III), Nd(III), and Yb(III), have been paid much attention for the potential use in the optical communications or laser systems. For the first time, the NIR-luminescent Ln(dbm)(3)phen complexes have been covalently bonded to the ordered mesoporous materials MCM-41 and SBA-15 via a functionalized phen group phen-Si (phen-Si = 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline; dbm = dibenzoylmethanate; Ln = Er, Nd, Yb). The synthesis parameters X = 12 and Y = 6 h (X denotes Ln(dbM)(3)(H2O)(2)/phen-MCM-41 molar ratio or Ln(dbM)(3)(H2O)(2)/phenSBA-15 molar ratio and Y is the reaction time for the ligand exchange reaction; phen-MCM-41 and phenSBA-15 are phen-functionalized MCM-41 and SBA-15 mesoporous materials, respectively) were selected through a systematic and comparative study. The derivative materials, denoted as Ln(dbM)(3)phen-MCM-41 and Ln(dbm)(3)phen-SBA-15 (Ln = Er, Nd, Yb), were characterized by powder X-ray diffraction, nitrogen adsorption/desorption, Fourier transform infrared (FT-IR), elemental analysis, and fluorescence spectra. Upon excitation of the ligands absorption bands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions.

A novel way to synthesize high regular and periodic organic mesoporous silicas

Organic mesoporous silicas (OMSs) were synthesized in the presence of urea via one-pot synthesis method, in which tetraethyl orthosilicate (TEOS) and 3-aminopropyltriethoxysilica (APTES) were used as the silica resources, non-ionic surfactant was used as the template. XRD results showed that the average periodic mesopore sizes of OMSs in the presence of urea were larger than those in the absence of urea. It was also found that the pore sizes of the products in the presence of urea distributed more narrowly than those in the absence of urea, and the contents of organosiloxane incorporated into OMSs, the pore wall thicknesses, the pore volumes and the surface areas of the products all increased with the use of urea. This shows a novel way to synthesize high regular and periodic organic mesoporous silicas.