Exfoliated graphite oxide (GO) sheets with hydroxyl groups and amine groups on the surface were prepared by modification of graphite. Atom transfer radical polymerization (ATRP) initiator molecules were grafted onto the GO sheets by reactions of 2-bromo-2-methylpropionyl bromide with hydroxyl groups and amine groups. Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) chains on the surface of GO sheets were synthesized by in-situ ATRP. X-ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy (TEM) results all demonstrated that polymer chains were successfully produced. After grafting of PDMAEMA, the dispersity of GO sheets in solvents was improved significantly. Poly(ethylene glycol dimethacrylate-co-methacrylic acid) particles were deposited on GO sheets via hydrogen bonding between MAA units on polymer particles and amine groups of PDMAEMA. TEM and scanning electron microscopy were used to characterize the structure of the nanocomposites.
A facile synthesis is reported of two‐dimensional (2D) bimetallic (Fe/Co=1:2) metal–organic frameworks (MOF, ca. 2.2 nm thick) via simple stirring of the reaction mixture of Fe/Co salts and 1,4‐benzene dicarboxylic acid (1,4‐BDC) in the presence of triethylamine and water at room temperature. The mechanism of the 2D, rather than bulk, MOF was revealed by studying the role of each component in the reaction mixture. It was found that these 2D MOF‐Fe/Co(1:2) exhibited excellent electrocatalytic activity for the oxygen evolution reaction (OER) under basic conditions. The electrocatalytic mechanism was disclosed via both experimental results and density functional theory (DFT) calculation. The 2D morphology and co‐doping of Fe/Co contributed to the superior OER performance of the 2D MOF‐Fe/Co(1:2). The simple and efficient synthetic method is suitable for the mass production and future commercialization of functional 2D MOF with low cost and high yield.
Shape amphiphiles with distinct shapes and amphiphilic properties can be used as fundamental building blocks in the fabrication of novel structures and advanced materials. In this research synthesis and selfassembly of monotethered single-chain nanoparticle shape amphiphiles are reported. Poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (PDMAEMA-b-PS) was synthesized by two-step reversible addition− fragmentation chain transfer (RAFT) polymerization. The PDMAEMA blocks were intramolecularly cross-linked by 1,4-diiodobutane (DIB) at significantly low concentrations, and PS-tethered PDMAEMA single-chain nanoparticles were prepared. Gel permeation chromatograph, 1 H NMR and transmission electron microscopy results all indicated successful synthesis of the structures. The controlled self-assembly of the shape amphiphiles in selective solvents was investigated. Depending on the size of the single-chain nanoparticles, the shape amphiphiles self-assemble into strawberry-like micelles, a structure with single-chain nanoparticles in the corona and PS in the core, or vesicles in aqueous solutions. Similar to the self-assembled structures in aqueous solution, the morphology of the aggregates in methanol changes from micellar structure to vesicular structure with the decrease of the PDMAEMA single-chain nanoparticles size. In cyclohexane, the shape amphiphiles self-assemble into bunchy micelles with single-chain nanoparticles in the cores and linear PS in the coronae.
Carboxyl groups at the periphery of reduced graphene oxide (RGO) sheets are converted to amine groups by reaction with N-hydroxysuccinimide and 1,3-diaminopropane, and a free-radical polymerization initiator is anchored to the RGO sheets. Poly(acrylamide) (PAM) polymer brushes on RGO sheets (RGO/PAM) are synthesized by in situ free-radical polymerization. The heavy metals, Pb(II), and the benzenoid compounds, methylene blue, (MB) were selected and adsorbed by RGO/PAM composites, and the adsorption capacity of RGO/PAM for Pb(II) and MB was measured. The experimental data of RGO/PAM isotherms for Pb(II) and MB followed the Langmuir isotherm model. The RGO/PAM displays adsorption capacities as high as 1000 and 1530 mg/g for Pb(II) and MB, respectively, indicating RGO/PAM is a good adsorbent for the adsorption of Pb(II) and MB. The adsorption kinetics of Pb(II) and MB onto RGO/PAM can be well fitted to the pseudo-second-order model. The adsorption processes of Pb(II) and MB onto RGO/PAM are spontaneous at 298, 308, and 318 K.
Exfoliated graphene oxide (GO) sheets with hydrophilic functional groups on the surface were prepared by the oxidation of graphite. Because of the hydrophilic groups on the sheets and the hydrophobic carbon surface, GO sheets were located at the oil-water interface and could be used as a stabilizer in Pickering emulsions. After the Pickering emulsion polymerization of styrene, PS colloidal particles with GO sheets on the surface were prepared. The size of the GO sheets exerts an important influence on the preparation of PS colloidal particles. Small GO sheets located at the liquid-liquid interface and GO-stabilized PS colloidal particles were prepared; however, for large GO sheets, smaller PS colloidal particles prepared on the GO surface were observed. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the colloidal particles. TEM, SEM, and XPS results all suggest the successful preparation of GO-stabilized PS colloidal particles.
Preparation and characterization of poly(N‐isopropylacrylamide) (PNIPAM) polymer brushes on the surfaces of reduced graphene oxide (RGO) sheets based on click chemistry and reversible addition‐fragmentation chain transfer (RAFT) polymerization was reported. RGO sheets prepared by thermal reduction were modified by diazonium salt of propargyl p‐aminobenzoate, and alkyne‐functionalized RGO sheets were obtained. RAFT chain transfer agent (CTA) was grafted to the surfaces of RGO sheets by click reaction. PNIPAM on RGO sheets was prepared by RAFT polymerization. Fourier transform‐infrared spectroscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and transmission electron microscopy (TEM) results all demonstrated that RAFT CTA and PNIPAM were successfully produced on the surfaces of RGO sheets. Nanosized PNIPAM domains on RGO sheets were observed on TEM. Micro‐DSC result indicated that in aqueous solution PNIPAM on RGO sheets presented a lower critical solution temperature at 33.2 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
Brush macromolecules having poly(l-lactide) (PLLA) and poly(styrene) (PS) side chains were prepared on the backbone of partially esterified poly(2-hydroxyethyl methacrylate) (PHEMA) by using a combination of atom transfer radical polymerization (ATRP) and ring-opening polymerization. The number-average degrees of polymerization of PLLA side chains and PS side chains were determined by 1H NMR spectroscopy, and the apparent molecular weights of the brush molecules were measured by gel permeation chromatography. The relationship between the crystallization of PLLA with PLLA and PS side chain lengths was investigated. Inside a brush molecule due to the unfavorable interaction between PLLA and PS two phases were formed. Brush molecules adsorbed on mica tend to make a starlike conformation; however, they change to a globular conformation after thermal treatment.
The amphiphilic poly(methyl methacrylate-block-2-(dimethylamino)ethyl methacrylate) (PMMA-b-PDMAEMA) block copolymer brushes on the surface of clay layers were synthesized by in situ atom transfer radical polymerization. X-ray diffraction results indicate that both exfoliated and intercalated structure can be found in the nanocomposites. The block copolymer brushes can make different nanopatterns on the surface of clay layers after treatment in different solvents. After treatment in tetrahydrofuran block copolymer brushes form lamella structure on the surface, and after treatment in water surface micelles and wormlike structure can be observed. PMMA colloid particles armored by clay nanocomposites were prepared by suspension polymerization. Transmission electron microscopy and scanning electron microscopy were used to characterize the structure and morphology of the colloid particles. Colloid particles with clay layers around the surface can be observed. X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of the colloid particles. N1s binding energy of PDMAEMA blocks on the surface of clay layers was detected by XPS. The two peaks of the N1s binding energy indicate two different nitrogen environments on the surface of clay layers. The peak with a lower binding energy is characteristic of neutral nitrogen on PDMAEMA blocks, and the peak with a higher binding energy is attributed to protonated nitrogen on PDMAEMA blocks.
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