Kakarla Raghava Reddy

Edge-enriched graphene quantum dots for enhanced photo-luminescence and supercapacitance

Graphene quantum dots (GQDs) with their edge-bound nanometer-size present distinctive properties owing to quantum confinement and edge effects. We report a facile ultrasonic approach with chemical activation using KOH to prepare activated GQDs or aGQDs enriched with both free and bound edges. Compared to GQDs, the aGQDs we synthesized had enhanced BET surface area by a factor of about six, the photoluminescence intensity by about four and half times and electro-capacitance by a factor of about two. Unlike their non-activated counterparts, the aGQDs having enhanced edge states emit enhanced intense blue luminescence and exhibit electrochemical double layer capacitance greater than that of graphene, activated or not. Apart from their use as part of electrodes in a supercapacitor, the superior luminescence of aGQDs holds potential for use in biomedical imaging and related optoelectronic applications.

Carbon functionalized TiO2 nanofibers for high efficiency photocatalysis

TiO2 nanofibers (30–50 nm diameter), fabricated by the electro-spinning process, were modified with organo-silane agents via a coupling reaction and were grafted with carbohydrate molecules. The mixture was carbonized to produce a uniform coating of amorphous carbon on the surface of the TiO2 nanofibers. The TiO2@C nanofibers were characterized by high resolution electron microscopy (HRTEM), x-ray diffraction (XRD), x-ray photoelectron (XPS), Fourier transform infrared (FTIR) and UV-vis spectroscopy. The photocatalytic property of the functional TiO2 and carbon nanocomposite was tested via the decomposition of an organic pollutant. The catalytic activity of the covalently functionalized nanocomposite was found to be significantly enhanced in comparison to unfunctionalized composite and pristine TiO2 due to the synergistic effect of nanostructured TiO2 and amorphous carbon bound via covalent bonds. The improvement in performance is due to bandgap modification in the 1D co-axial nanostructure where the anatase phase is bound by nano-carbon, providing a large surface to volume ratio within a confined space. The superior photocatalytic performance and recyclability of 1D TiO2@C nanofiber composites for water purification were established through dye degradation experiments.

High-yield aqueous phase exfoliation of graphene for facile nanocomposite synthesis via emulsion polymerization

Aqueous phase exfoliation was developed for producing high-yield graphene nanosheets from expanded graphite (EG). The process included ultrasonication with sodium dodecyl sulfate (SDS) emulsion in aqueous phase. The high throughput exfoliation process was characterized by UV-vis spectroscopy, transmission electron microscopy (TEM) and electrical impedance spectroscopy (EIS). Controlled sonication experiments revealed that optimum exfoliation corresponds to maxima in UV-vis spectra. TEM results showed that the exfoliated graphene comprised nanoflakes having ≤5 layers (~60%) and ≤10 layers for 90% of the product. The potential use of this highly dispersed graphene was demonstrated by one-pot synthesis of graphene/polymer composite via in situ emulsion polymerization with styrene. The integrated role of SDS included adsorption and exfoliation of graphite, dispersion of graphene produced and assisting with micelle formation in emulsion. The high surface area graphene nanosheets as dispersed phase in polymeric nanocomposites showed significant improvement in thermal stability and electrical conductivity.

Graphene Modified Lipophilically by Stearic Acid and its Composite With Low Density Polyethylene

Graphene, prepared by the thermal reduction of graphite oxide (GO), was modified with stearic acid to enhance its lipophilicity. A novel method, using the intrinsic epoxy groups on the graphene, was utilized for reaction with stearic acid to minimize the negative impact of the normal functionalization method on the π-electronic system of graphene. Gravimetric analysis, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) showed that the stearic acid was effectively attached to the graphene. In addition, Raman spectroscopy and electric conductivity of the graphene showed that this novel modification method, utilizing intrinsic defects, did not damage the π-electronic system of the sp2 bonded carbons. The dispersion of graphene in a low density polyethylene (LDPE) matrix was enhanced; consequently, the reinforcing effect in tensile testing was improved by the lipophilic modification. The crystallization behavior observed by differential scanning calorimetry (DSC) showed that the crystallization of LDPE was hindered by dispersed graphene, more evidently when dispersed uniformly.

Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization

In situ emulsion polymerization was employed for synthesizing carbon nanotube (CNT) composites in a colloidal system with poly(styrene) or PS to form nanostructured brush. CNTs were initially functionalized with oleic acid, followed by silanization with (3-aminopropyl) triethoxysilane to impart cross-linking properties. Styrene monomers were efficiently grafted to surface modified CNT via emulsion polymerization with variable CNT concentrations. FTIR analyses of the functionalized CNT and PS/CNT composites confirmed the bond formation and effectiveness of the developed experimental method. X-ray photoelectron spectroscopy confirmed the presence of the desired bonds and the composition of the composites. Structural properties of the composites characterized by TEM confirmed excellent deagglomeration and dispersion of CNTs in PS/CNT composite. Thermal characteristics from TGA and DSC data showed enhanced properties for the nanocomposites as a function of the CNT content. BET measurements indicated significant improvements in surface area and pore volume with enhancements in gas sorption for the polymer nanocomposites.

Compatibility of Thermally Reduced Graphene with Polyesters

ABSTRACT The compatibility of thermally reduced graphene (TRG) with multiblock copolyesters, composed of poly(butylene terephthalate) (PBT) segments and poly(tetramethylene ether) glycol segments, was examined in detail. The morphology observed by optical microscopy and scanning electron microscopy showed that the compatibility was enhanced with increasing content of the PBT segment in the polyester. This compatibility behavior was analyzed quantitatively, by using the percolation threshold of electrical conductivity, and then further analyzed by using the Hansen solubility parameters to provide a general quantitative guideline to predict the compatibility of TRG with various polymers. The results suggest that the total solubility parameter, δT, value of TRG is larger than 24.0 (MPa)½, and thus that the compatibility with polymer is enhanced as the δT value of a polymer increases toward 24.0 (MPa)½. However, this prediction does not fit well in the presence of a comonomer such as acrylic acid, which has a high tendency to hydrogen bond with itself.

Nanoarchitectured Graphene-Organic Frameworks (GOFs): Synthetic Strategies, Properties, and Applications

Graphene-organic frameworks (GOFs) is a new class of graphene-based materials in which structure and properties can be designed by controlling the length and concentration of organic ligands, comparable to their tunable metal-organic frameworks (MOFs) counterpart. The structural properties (e.g., surface area, pore volume) and physico-chemical properties (e.g., electronic, thermal, and mechanical) of GOFs can be tuned based on the synthetic conditions. Such GOFs are promising as the next generation of novel materials for a wide range of potential applications such as H2 storage, electronic devices, sensors, drug carriers, etc. Here we report a review summarizing synthetic strategies, properties, and applications of GOFs.