A novel approach to constructing three-dimensional (3D) highly ordered structural polyaniline-graphene bulk hybrid materials was proposed for high performance supercapacitor electrodes, in which a functional molecule, sulfonated triazine (ST), was introduced and adsorbed on graphene sheets via hydrogen bonding and p-p stacking interactions. The aim of adding ST is to achieve better dispersion of graphene nanosheets in water, and subsequently induce heterogeneous nucleation of polyaniline (PANI) through electrostatic interactions. Thus, the PANI nanorods were impelled to grow vertically on both surfaces of the individual sulfonated triazine functional graphene nanosheets (STGNS) via in situ chemical oxidative polymerization of aniline in aqueous solution. The formation mechanism of well-controlled PANI nanorod array-sulfonated triazine functional graphene nanosheet (PANI-STGNS) hybrid materials was investigated in detail using a combination of UV-vis, FTIR, Raman spectroscopy and XRD. The optimized PANI-STGNS10 bulk hybrid material possesses a specific capacitance as high as 1225 F g À1 at 1 A g À1 , together with outstanding rate capability and cycling stability, which are essential for its application in high performance supercapacitor electrodes.
A series of soluble polyhedral oligomeric silsesquioxane (POSS) based inorganic−organic hybrid nonlinear optical materials with different architectures, such as dumbbell-type, bead-type and network-type structure, were prepared based on the hydrosilylation addition reaction of multifunctional octahydridosilsesquioxane (T
8
H
) with different azobenzene chromophore monomers. These resultant hybrid composites are soluble in common organic solvents such as tetrahydrofuran, toluene, and chloroform, and exhibit good film-forming ability. Their structures and properties were characterized and evaluated with IR, 1H NMR, 29Si NMR, TGA, DSC, optical limiting measurement and Z-scan technique, respectively. The results show that the structure of these resultant hybrids can be effectively tuned by simply varying the feed ratio and molecular structure of organic chromophore monomers. The incorporation of inorganic POSS into organic azobenzene chromophore has endowed the hybrids with well optical limiting properties and high thermal stability. Simultaneously, the relationship between molecular structure and properties of these hybrids were investigated in detail.
To further investigate the influence of dye architecture
on dye-sensitized
solar cell (DSSC) performance, some near-infrared absorbing quinoline-based
squaraine dyes (4a, 4b, and 4c) with different conjugated degrees carrying carboxylic or sulfonic
groups as anchoring groups were designed, prepared, and applied as
sensitizers in solar cells. The photophysical and photochemical studies
showed that photoelectric conversion efficiencies (η) are significantly
affected by molecular structures; i.e., η of 4c with the strongest polarity and anchoring ability and the longest
π electron conjugated degree was two times more than that of 4b and six times more than that of 4a. That is,
the molecules with smaller optical band gap and higher molar absorption
coefficient will possess better light-harvesting properties and enhanced
conversion efficiency. Furthermore, all excited state orbitals relevant
for the π–π electron transition both in 4b and 4c are delocalized over the anchoring groups, ensuring
a strong electronic coupling to the conduction band of TiO2 and hence a fast electron transfer.
A series of new molecular hybrids with stilbene chromophore (H1-H4) are prepared by hydrosilylation of octahydridosilsesquioxane (T 8 H ). All these stilbene-containing hybrid materials are soluble in common organic solvents, such as chloroform, toluene, THF, and 1,2-dichloroethane, and possess good film-forming properties. Their structures and properties are characterized and evaluated by FT-IR, NMR, UV, PL, TGA, DSC, nonlinear optical (NLO), and optical limiting (OL) analyses. The results show that the thermal decomposition temperatures (T d , 5 mass % loss) of the hybrids are 20-60 °C greater than their corresponding stilbene monomers, and the hybrids show obvious nonlinear absorption (β up to 2.56 Â 10 -11 m/W) and optical limiting properties. The larger excited-state absorption cross sections than corresponding ground-state absorption cross sections of the hybrids indicate that reverse saturable absorption is a major mechanism responsible for the optical limiting of the hybrids.
A novel BODIPY-based fluorescent thermometer, which shows a lysosome-targeting property, was successfully prepared. Due to the electron-donating ability of the oligo(ethylene glycols), the photoinduced electron-transfer pathway from morpholine to BODIPY dye is blocked. The fluorescence of the thermometer quenched by intramolecular rotation at room temperature was progressively enhanced during heating due to the increased microviscosity around the fluorophore.
Poly(1-alkyne)s containing azobenzene pendants with different spacer lengths and ring substitutents-{HCaC[(CH 2) m COO-C 6 H 4-NaN-C 6 H 4-NO 2 ]} n-P1(m) mZ3, 8 and-{HCaC[(CH 2) m COO-C 6 H 3-o-Br-NaN-C 6 H 4-NO 2 ]} n-P2(m) mZ3, 8} are designed and synthesized. The polymers are prepared in satisfactory yields with high molecular weights (M w up to 3.3!10 4 Da) by [Rh(nbd)Cl] 2-Et 3 N in THF or dioxane. Their structures and properties are characterized and evaluated by IR, UV, NMR, TGA, nonlinear optical and optical limiting analyses. All the polymers are completely soluble in common organic solvents and lose 5% of their weights at temperatures of w270 8C. The spacer length and the pendant substitutent affect the nonlinear optical and optical limiting properties of the polymers, with 1(3) showing superior properties than its counterparts 1(8) and 2(3) with long methylene spacers and bromide substitutents on the azobenzene pendants, respectively.
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