The Photocatalysis-Enhanced TiO2@HPAN Membrane with High TiO2 Surface Content for Highly Effective Removal of Cationic Dyes.

The elimination of dye pollutants from wastewater is a significant concern that has prompted extensive research into the development of highly efficient photocatalytic membranes. A novel method was proposed to prepare photocatalysis-enhanced poly(acrylonitrile-methyl acrylate) (PAN-based) membranes in this study. In detail, the blended membrane containing SiO2@TiO2 nanoparticles with a shell-core structure was first prepared via thermal-induced phase separation. The SiO2 nanoshells were dissolved, and the released TiO2 nanoparticles migrated to the membrane surface during a simple hydrolysis process, which prevents the TiO2 nanoparticles from directly contacting or interacting with the polymer matrix. The hydrogen bonds bind the exposed TiO2 with the PAN membrane surface, resulting in the formation of the TiO2@HPAN hybrid membrane. The photocatalytic efficiency of the TiO2@HPAN membrane doubled compared with that of nonhydrolyzed membranes. In the presence of UV light, the hybrid membrane can degrade 99.8% of methylene blue solution in less than 2 h, compared to only 86.1% for the blended membranes. Further, the TiO2@HPAN membrane showed excellent photocatalytic activity for cationic dyes due to electrostatic attraction. Moreover, the high-flux recovery rate and recycling stability of the TiO2@HPAN membrane lead to an excellent antifouling property. The facile preparation method proposed in this work shows extraordinary potential for the development of highly efficient selective photocatalytic materials for cationic dyes to be used in wastewater treatment applications.

Self-assembly synthesis, structural features, and photophysical properties of dilanthanide complexes derived from a novel amide type ligand: energy transfer from Tb(III) to Eu(III) in a heterodinuclear derivative.

A novel amide type ligand benzyl-N,N-bis[(2'-furfurylaminoformyl)phenoxyl)ethyl]-amine (L) has been designed and applied for the self-assembly generation of homodinuclear lanthanide coordination compounds [Ln2(µ2-L)2(NO3)6(EtOH)2] [Ln = Eu (1), Tb (2), and Gd (3)] and a heterodinuclear derivative [EuTb(µ2-L)2(NO3)6(EtOH)2] (4). All the complexes have been characterized by the X-ray single-crystal diffraction analyses. They are isostructural, crystallize in a monoclinic space group P21/c, and form [2 + 2] rectangular macrocycle structures. Compound 4 is the first example of a [2 + 2] rectangular macrocycle heterodinuclear EuTb complex assembled from an amide type ligand. In 4, the discrete 0D dimeric [EuTb(µ2-L)2(NO3)6(EtOH)2] units are extended, via the multiple N-H···O hydrogen bonds, into a 2D supramolecular network that has been topologically classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology. The triplet state ((3)ππ*) of L studied by the Gd(III) complex 3 demonstrated that the ligand beautifully populates Tb(III) emission (Φ = 52%), whereas the corresponding Eu(III) derivative 1 shows weak luminescence efficiency (Φ = 0.7%) because the triplet state of L has a poor match with (5)D1 energy level of Eu(III). Furthermore, the photoluminescent properties of heterodinuclear complex 4 have been compared with those of the analogous homodinuclear compounds. The quantum yield and lifetime measurements prove that energy transfer from Tb(III) to Eu(III) is being achieved, namely, that the Tb(III) center is also acting to sensitize the Eu(III) and enhancing Eu(III) emission in 4.

Enhanced separation of potassium ions by spontaneous K+-induced self-assembly of a novel metal-organic framework and excess specific cation-π interactions.

A novel metal-organic framework (MOF) was fabricated by spontaneous K(+)-induced supramolecular self-assembly with the embedded tripodal ligand units. When the 3D ligand was loaded onto Fe3O4@mSiO2 core-shell nanoparticles, it could effectively separate K(+) ions from a mixture of Na(+), K(+), Mg(2+), and Ca(2+) ions through nanoparticle-assisted MOF crystallization into a Fe3O4@mSiO2@MOF hybrid material. Excess potassium ions could be extracted because of the specific cation-π interaction between K(+) and the aromatic cavity of the MOF, leading to enhanced separation efficiency and suggesting a new application for MOFs.

Anion-induced structures and luminescent properties of chiral lanthanide-organic frameworks assembled by an achiral tripodal ligand.

To confirm how different anions influence sup-ramolecular self-assembly of lanthanide-organic frameworks (LnOFs) as well as their luminescent properties, a new flexible achiral tripodal ligand, 1,1,1-tris-{[(2'-benzylaminoformyl)phenoxyl]methyl}ethane (L) and the LnOFs {[EuL(NO(3))(3)]·1.5CHCl(3)}(n) and [EuL(pic)(3)](n) have been designed and assembled. In the two LnOFs, {[EuL(NO(3))(3)]·1.5CHCl(3)}(n) demonstrates an unprecedented chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6(3), vertex symbol 6·6·6) topological network, and [EuL(pic)(3)](n) confirms an unusual chiral LnOF with three-dimensional (3D) (10,3)-a (srs, SrSi(2), Schläfli symbol 10(3), vertex symbol 10(2)·10(4)·10(4)) topological framework. Also the anion-induced structures and energy transfer processes in the luminescence behavior of the two LnOFs were discussed in detail.

Synthesis and luminescent properties of lanthanide complexes with structurally related novel multipodal ligands.

To explore the relationship between the structure of the ligands and the luminescent properties of the lanthanide complexes, a series of lanthanide nitrate complexes with two novel structurally related multipodal ligands, 1,3-bis{[(2'-(2-picolylaminoformyl))phenoxyl]methyl}benzene (L(I)) and 1,2-bis{[(2'-(2-picolylaminoformyl))phenoxyl]methyl}benzene (L(II)), have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Eu(III) and Tb(III) nitrate complexes in solid state and the Tb(III) nitrate complexes in solvents were investigated at room temperature. Under the excitation of UV light, these complexes exhibited characteristic emissions of central metal ions. The lowest triplet state energy levels T(1) of these ligands both match better to the lowest resonance energy level of Tb(III) than to Eu(III) ion. The influence of the structure of the ligands on the luminescent intensity of the complexes was also discussed.

One-step electrospinning cellulose nanofibers with superhydrophilicity and superoleophobicity underwater for high-efficiency oil-water separation.

Cellulose nanofibers have been widely applied in many fields because of its unique advantages. However, it is a challenge to prepare cellulose nanofibers by electrospinning directly owing to the special molecular structure of cellulose. This limits the practical applications of cellulose nanofibers. In this work, cellulose nanofibers were successfully prepared directly by design of new electrospinning receiving device and optimization of process parameters. The as-prepared cellulose nanofibers exhibit good oil-water separation performances. Driven solely by gravity, the separation flux of the cellulose nanofibers for mixture of oil and water reaches 34,300.6 L m-2 h-1, and the separation flux and efficiency for surfactant-stabilized emulsion of oil and water reach 2503.7 L m-2 h-1 and over 98.3%, respectively. The as-prepared cellulose nanofibers also exhibit good mechanical properties and reusability. The breaking strength of the cellulose nanofibers can reach 148.2 cN. The separation fluxes of cellulose nanofibers for mixtures and emulsions of oil and water can be maintained 99.7% and 86.3% of the initial value after being used for 20 times. Furthermore, the as-prepared cellulose nanofibers have good degradability. These properties render as-prepared cellulose nanofibers as promising materials with potential applications in oil-water separation.

Two selective fluorescent chemosensors for cadmium ions in 99% aqueous solution: the end group effect on the selectivity, DFT calculations and biological applications.

Two fluorescent chemosensors for cadmium ions, 2-(2-formylquinolin-8-yloxy)-N,N-diisopropylacetamide (FQDIPA) and 2-(2-formylquinolin-8-yloxy)-N,N-diphenylacetamide (FQDPA), were first assessed in 99% aqueous solutions. The sensor FQDIPA with an end group of an aliphatic amine can recognize Cd(2+) from other metal ions more selectively and sensitively than FQDPA with that of aromatic amines, which was further demonstrated by DFT calculations that were comparable to the experimental results. It is indeed the distinction between the end groups of these chemosensors that results in the variation of the energy difference between the LUMOs and HOMOs and the interaction energies of FQDIPA·Cd(2+) and FQDPA·Cd(2+). Furthermore, the living cell image experiment could also indicate that the FQDIPA is more suitable than the FQDPA in the practical applications in biological systems.

A novel luminescent chemosensor for detecting Hg(2+) based on the pendant benzo crown ether terbium complex.

A novel luminescent chemosensor for detecting Hg(2+) with high selectivity, based on a pendant benzo crown ether terbium complex, has been designed and prepared.