Natural microfibrils/regenerated cellulose-based carbon aerogel for highly efficient oil/water separation.

Cellulose-based carbon aerogels as biodegradable and renewable biomass materials have presented potential applications in oil/water separation. Herein, a novel carbon aerogel composed of natural microfibrils/regenerated cellulose (NM/RCA) was directly prepared by economical hardwood pulp as raw material using a novel co-solvent composed of deep eutectic solvent (DES) and N-methyl morpholine-N-oxide monohydrate (NMMO·H2O). In addition, the morphology and structure of the filiform natural microfibers could be remained after carbonized at 400 â„ƒ, which resulted in a low density (8-10 mg cm-3), high specific surface area (768.89 m2 g-1) and high sorption capability. In addition, the aerogel exhibited high compressibility, outstanding elasticity, excellent fatigue resistance, and recyclability (80.5% height recovery after repeating 100 cycles at the strain of 80%). Due to the morphology and composition of the carbonized microfiber surface, the superhydrophobic materials with a water contact angle of 151.5°, could sorb various oils and organic solvents with 65-133 times its own weight and maintain 91.9% sorption capacity after 25 cycles. In addition, the aerogels could achieve the continuous separation of carbon tetrachloride (CCl4) from water with a high flux rate of 11,718.8 L m-2 h-1. Therefore, our prepared NM/RCA aerogels are anticipated to have broad potential applications in oil purification and contaminant remediation.

Development of Adsorptive Membranes for Selective Removal of Contaminants in Water.

The presence of arsenic and ammonia in ground and surface waters has resulted in severe adverse effects to human health and the environment. Removal technologies for these contaminants include adsorption and membrane processes. However, materials with high selectivity and pressure stability still need to be developed. In this work, adsorbents and adsorptive membranes were prepared using nanostructured graphitic carbon nitride decorated with molecularly imprinted acrylate polymers templated for arsenate and ammonia. The developed adsorbent removed arsenate at a capacity and selectivity similar to commercial ion-exchange resins. Ammonia was removed at higher capacity than commercial ion exchange resins, but the adsorbent showed lower selectivity. Additionally, the prepared membranes removed more arsenate and ammonia than non-imprinted controls, even in competition with abundant ions in water. Further optimization is required to improve pressure stability and selectivity.

Nitrogen-Deficient Graphitic Carbon Nitride with Enhanced Performance for Lithium Ion Battery Anodes.

Graphitic carbon nitride (g-C3N4) behaving as a layered feature with graphite was indexed as a high-content nitrogen-doping carbon material, attracting increasing attention for application in energy storage devices. However, poor conductivity and resulting serious irreversible capacity loss were pronounced for g-C3N4 material due to its high nitrogen content. In this work, magnesiothermic denitriding technology is demonstrated to reduce the nitrogen content of g-C3N4 (especially graphitic nitrogen) for enhanced lithium storage properties as lithium ion battery anodes. The obtained nitrogen-deficient g-C3N4 (ND-g-C3N4) exhibits a thinner and more porous structure composed of an abundance of relatively low nitrogen doping wrinkled graphene nanosheets. A highly reversible lithium storage capacity of 2753 mAh/g was obtained after the 300th cycle with an enhanced cycling stability and rate capability. The presented nitrogen-deficient g-C3N4 with outstanding electrochemical performances may unambiguously promote the application of g-C3N4 materials in energy-storage devices.

In vitro and in vivo corrosion, mechanical properties and biocompatibility evaluation of MgF2-coated Mg-Zn-Zr alloy as cancellous screws.

Magnesium (Mg) and its alloys as biodegradable materials have received much attention in the orthopedics applications; however, the corrosion behavior of these metals in vivo remains challenging. In this work, a dense and nanoscale magnesium fluoride (MgF2) coating was deposited on the surface of Mg-Zn-Zr (MZZ) alloy cancellous screw. The MZZ cancellous screw with MgF2 coating maintained an integrated shape and high yield tensile stress after 30days immersion in SBF, comparing with the bare screw. Hydrogen releasing rate of the MZZ samples was suppressed at a lower level at the initial stage, which is in favour of the adhesion of the cells. And in vivo experiments indicated that MgF2-coated MZZ screws presented advantages in cytocompatibility, osteoconductivity and osteogenesis of cancellous bone in rabbits. Corrosion rate in vivo perfusion environment increased very slowly with time in long-term study, which was an opposite trend in vitro static immersion test. Moreover, maximum corrosion rate (CRmax), a critical calculation method of corrosion rate was introduced to predict fracture regions of the sample. The MZZ alloy with MgF2 coating possesses a great potential for clinical applications for internal fracture fixation repair.

Novel g-C3N4/CoO Nanocomposites with Significantly Enhanced Visible-Light Photocatalytic Activity for H2 Evolution.

Novel g-C3N4/CoO nanocomposite application for photocatalytic H2 evolution were designed and fabricated for the first time in this work. The structure and morphology of g-C3N4/CoO were investigated by a wide range of characterization methods. The obtained g-C3N4/CoO composites exhibited more-efficient utilization of solar energy than pure g-C3N4 did, resulting in higher photocatalytic activity for H2 evolution. The optimum photoactivity in H2 evolution under visible-light irradiation for g-C3N4/CoO composites with a CoO mass content of 0.5 wt % (651.3 µmol h-1 g-1) was up to 3 times as high as that of pure g-C3N4 (220.16 µmol h-1 g-1). The remarkably increased photocatalytic performance of g-C3N4/CoO composites was mainly attributed to the synergistic effect of the junction or interface formed between g-C3N4 and CoO.

Hafnium(IV) chloride complexes with chelating ß-ketiminate ligands: Synthesis, spectroscopic characterization and volatility study.

The synthesis and characterization of four new ß-ketiminate hafnium(IV) chloride complexes dichloro-bis[4-(phenylamido)pent-3-en-2-one]-hafnium (4a), dichloro-bis[4-(4-methylphenylamido)pent-3-en-2-one]-hafnium (4b), dichloro-bis[4-(4-methoxyphenylamido)pent-3-en-2-one]-hafnium (4c), and dichloro-bis[4-(4-chlorophenylamido)pent-3-en-2-one]-hafnium (4d) are reported. All the complexes (4a-d) were characterized by spectroscopic methods ((1)H NMR, (13)C NMR, IR), and elemental analysis while the compound 4c was further examined by single-crystal X-ray diffraction, revealing that the complex is monomer with the hafnium center in octahedral coordination environment and oxygens of the chelating N-O ligands are trans to each other and the chloride ligands are in a cis arrangement. Volatile trends are established for four new ß-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ΔHsub on the molecular weight (4a-c) and inductive effects from chlorine (4d).

Syntheses, characterizations and thermal analyses of four novel unsymmetrical ß-diketiminates.

Four novel unsymmetrical ß-diketiminates 2-(2,6-diisopropylphenyl)amino-4-(phenyl)imino-2-pentene (4a), 2-(2,6-diisopropylphenyl)amino-4-(4-methylphenyl)imino-2-pentene (4b), 2-(2,6-diisopropylphenyl)amino-4-(4-methoxyphenyl)imino-2-pentene (4c) and 2-(2,6-diisopropylphenyl)amino-4-(4-chlorophenyl)imino-2-pentene (4d) were synthesized with a 77-84% yield, and were characterized by spectroscopic methods ((1)H NMR, (13)C NMR, IR and mass spectrometry), elemental analysis, and X-ray single-crystal diffraction, respectively. Spectroscopic and X-ray single-crystal diffraction analyses determined the structures of the four ß-diketiminates. While thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) showed two distinct endothermic peaks for each ß-diketiminate at temperatures of 92.55°C and 221.50°C (4a), 93.51°C and 238.82°C (4b), 109.60°C and 329.22°C (4c), 115.43°C and 243.25°C (4d), respectively, corresponding to their melting and boiling points.

Enhanced electrochemical lithium storage by graphene nanoribbons.

Herein, we report the electrochemical Li intake capacity of carbonaceous one-dimensional graphene nanoribbons (GNRs) obtained by unzipping pristine multiwalled carbon nanotubes (MWCNTs). We have found that nanotubes with diameters of approximately 50 nm present a smaller reversible capacity than conventional mesocarbon microbead (MCMB) powder. Reduced GNRs improve the capacity only marginally over the MCMB reference but present a lower Coulombic efficiency as well as a higher capacity loss per cycle. Oxidized GNRs (ox-GNRs) outperform all of the other materials studied here in terms of energy density. They present a first charge capacity of approximately 1400 mA h g(-1) with a low Coulombic efficiency for the first cycle (approximately 53%). The reversible capacity of ox-GNRs is in the range of 800 mA h g(-1), with a capacity loss per cycle of approximately 3% for early cycles and a decreasing loss rate for subsequent cycles.

Molecular dynamics simulation of polyamidoamine dendrimer-fullerene conjugates: generations zero through four.

Previously the synthesis of the polyamidoamine (PAMAM) (G4)-C60 conjugate with a molar ratio of 1 : 30 was reported. Because PAMAM G4 has sixty-four primary amine groups, it was hypothesized that approximately two surface amine groups react with each fullerene molecule to form the conjugates. A computational energy minimization study of various G4 PAMAM-fullerene conjugates containing 1 dendrimer but different amounts of fullerenes shows excellent stability for the 1 : 30 dendrimer to fullerene product. Attempts to prepare other PAMAM dendrimer-fullerene (C60) conjugates, using generations G0-G3 of PAMAM and C60 via the same procedure in pyridine were not successful, possibly due to solubility differences. The same computational techniques used to study the G4 conjugates were then used to determine (1) the stability of the G0-G3 conjugates (with a 2 : 1 primary amine to fullerene ratio), and (2) their solubility in pyridine compared to the (G4)-C60 conjugate. The findings allow for a better understanding of structure-property relationships of these nano-hybrid materials, through investigation of the molecular shape and radius of gyration. The findings reported herein may lead to improved syntheses of fullerene-dendrimer conjugates of various sizes and a better understanding of their nanoscopic structures and topographical influences.

Facile synthesis of tin oxide nanoparticles stabilized by dendritic polymers.

Tin(IV) oxide nanoparticles were synthesized via the reaction of carbon dioxide with stannate ions immobilized by dendritic polymers. For PAMAM and PPI dendrimer hosts, resultant nanoparticle diameters were 2.5-3 nm; 3-3.5 nm nanoparticles resulted from use of a poly(ethyleneimine) hyperbranched polymer. Our conditions represent the only precedent for SnO2 nanoparticulate growth using dendritic architectures, as well as a novel application for CO2 as a reactive gas for the controlled growth of metal oxide nanoparticles.

Chloro[N,N'-ethylenediiminobis(acetylacetonato)]gallium(III).

In the title compound, [Ga(C12H18N2O2)Cl], the Ga atom is coordinated to a Cl atom and the two imine N and two enolate O atoms of the Schiff base ligand. The literature reveals few examples of a five-coordinate GaO2N2Cl environment, and only two where both the N and the O atoms are contained within the same ligand. This configuration has the effect of constraining the complex into a square-pyramidal geometry with less distortion than if formed by two or more ligands. The Ga-N and Ga-O distances are within the ranges expected for Ga-Schiff base derivatives. This compound is also the first group 13 complex containing the N,N'-ethylenebis(acetylacetoneimine) (acacen) ligand.

Preparation of fullerene-shell dendrimer-core nanoconjugates.

Generation 4 amine-terminated polyamidoamine dendrimer (PAMAM G4) was allowed to react with an excess of buckminsterfullerene (C60) to form a nanoconjugate containing a PAMAM core and C60 shell. The PAMAM-C60 conjugate was characterized by MALDI-TOF, TGA, UV-vis, and IR spectroscopy. Approximately thirty shell fullerenes surround each dendrimer core. The conjugates catalyze photooxidation of thioanisole by generation of singlet oxygen (1O2). The oxidation reactions occur in both organic and aqueous solvents, but the reactivity is enhanced in aqueous solution, possibly due to a nanoreactor effect resulting from diffusion of hydrophobic reactant molecules into dendrimer cavities.

Low-temperature growth of carbon nanotubes from the catalytic decomposition of carbon tetrachloride.

Multiwall carbon nanotubes (MWNTs) were synthesized via the decomposition of CCl4 in supercritical CO2 at 175 degrees C and 27.6 MPa using an iron-encapsulated dendrimer as a growth catalyst. The average diameter of resultant nanotubes was 20-25 nm, obtained after a 24-h reaction time. Our conditions represent the first application for CX4 precursors, as well as the lowest-reported temperature regime for carbon nanotube growth, allowing the use of other temperature-sensitive catalytic substrates.