Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Effect of Magnetic Field on Photoresponse of Cobalt Integrated Zinc Oxide Nanorods

Cobalt integrated zinc oxide nanorod (Co-ZnO NR) array is presented as a novel heterostructure for ultraviolet (UV) photodetector (PD). Defect states in Co-ZnO NRs surface induces an enhancement in photocurrent as compared to pristine ZnO NRs PD. Presented Co-ZnO NRs PD is highly sensitive to external magnetic field that demonstrated 185.7% enhancement in response current. It is concluded that the opposite polarizations of electron and holes in the presence of external magnetic field contribute to effective separation of electron hole pairs that have drifted upon UV illumination. Moreover, Co-ZnO NRs PD shows a faster photodetection speed (1.2 s response time and 7.4 s recovery time) as compared to the pristine ZnO NRs where the response and recovery times are observed as 38 and 195 s, respectively.

Ultrafine graphene oxide-CoFe2O4 nanoparticle composite as T-1 and T-2 contrast agent for magnetic resonance imaging

Graphene oxide-CoFe2O4 nanoparticle composites were synthesized using a two step synthesis method in which graphene oxide was initially synthesized followed by precipitation of CoFe2O4 nanoparticles in a reaction mixture containing graphene oxide. Samples were extracted from the reaction mixture at different times at 80 degrees C. All the extracted samples contained CoFe2O4 nanoparticles formed over the graphene oxide. It was observed that the increase in the reflux time significantly increased the saturation magnetization value for the superparamagnetic nanoparticles in the composite. It was also noticed that the size of the nanoparticles increased with increase in the reflux time. Transverse relaxivity of the water protons increased monotonically with increase in the reflux time. Whereas, the longitudinal relaxivity value initially increased and then decreased with the reflux time. Graphene oxide-CoFe2O4 nanoparticle composites also exhibit biocompatibility towards the MCF-7 cell line.

Facile synthesis of Graphene Oxide/Double-stranded DNA composite liquid crystals and Hydrogels

Investigation of the interactions between graphene oxide (GO) and biomolecules is very crucial for the development of biomedical applications based on GO. This study reports the first observation of the spontaneous formation of self-assembled liquid crystals and three-dimensional hydrogels of graphene oxide with double-stranded DNA by simple mixing in an aqueous buffer media without unwinding double-stranded DNA to single-stranded DNA. The GO/dsDNA hydrogels have shown controlled porosity by changing the concentration of the components. The strong binding between dsDNA and graphene is proved by Raman spectroscopy.

Nitrogen-assisted electroless assembling of 3D nanodendrites consisting of Pd and N-doped carbon nanoparticles as bifunctional catalysts

We report a facile synthesis of three-dimensional (3D) nanodendrites of Pd nanoparticles (NPs) and nitrogen-doped carbon NPs (N-CNPs) by electroless deposition of Pd2+ ions. N-CNPs being an electron-enriched material act as a reducing agent. Moreover, the availability of a variety of nitrogen species in N-CNPs promotes the open arm structure as well as stabilizes the oriented 3D assembly of primary Pd NPs. The dendrites exhibit superior catalytic activity for methanol (0.5 M) oxidation in alkaline media (1 M NaOH) which is ascribed to the large electrochemical active surface area and the enhanced mass activity with repeated use. Further mass activity improvement has been realized after acid-treatment of dendrites which is attributed to the increment in the -OH group. The dendrites show higher mass activity (J(f) similar to 653 A g(-1)) in comparison with a commercial Pt-carbon/Pd-carbon (Pt-C/Pd-C) catalyst (J(f) similar to 46 and 163 A g(-1), respectively), better operational stability, superior CO tolerance with I-f/I-b (similar to 3.7) over a commercial Pt-C/Pd-C catalyst (I-f/I-b similar to 1.6 and 1.75, respectively) and may serve as a promising alternative to commercial Pt-C catalysts for anode application in alkaline fuel cells. To ensure the adaptability of our 3D-nanodendrites for other catalytic activities, we studied 4-nitrophenol reduction at room temperature. The 3D-nanodendrites show excellent catalytic activity toward 4-nitrophenol reduction, as well.

Engineering a multi-biofunctional composite using poly(ethylenimine) decorated graphene oxide for bone tissue regeneration

Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly( e-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was approximate to 50% better than GO. Remarkably, 5% GO_ PEI was as potent as soluble osteoinductive factors. Increased adsorption of osteogenic factors due to the amine and oxygen containing functional groups on GO_ PEI augment stem cell differentiation. GO_ PEI was also highly efficient in imparting bactericidal activity with 85% reduction in counts of E. coli colonies compared to neat PCL at 5% filler content and was more than twice as efficient as GO. This may be attributed to the synergistic effect of the sharp edges of the particles along with the presence of the different chemical moieties. Thus, GO_ PEI based polymer composites can be utilized to prepare bioactive resorbable biomaterials as an alternative to using labile biomolecules for fabricating orthopedic devices for fracture fixation and tissue engineering.

Electrochemical deposition of manganese oxide-phosphate-reduced graphene oxide composite and electrocatalysis of the oxygen evolution reaction

A composite of manganese oxide and reduced graphene oxide (rGO) is prepared in a single step electrochemical reduction process in a phosphate buffer solution for studying as an electrocatalyst for the oxygen evolution reaction (OER). The novel composite catalyst, namely, MnOx-Pi-rGO, is electrodeposited from a suspension of graphene oxide (GO) in a neutral phosphate buffer solution containing KMnO4. The manganese oxide incorporates phosphate ions and deposits on the rGO sheet, which in turn is formed on the substrate electrode by electrochemical reduction of GO in the suspension. The OER is studied with the MnOx-Pi-rGO catalyst in a neutral phosphate electrolyte by linear sweep voltammetry. The results indicate a positive influence of rGO in the catalyst. By varying the ratio of KMnO4 and GO in the deposition medium and performing linear sweep voltammetry for the OER, the optimum composition of the deposition medium is obtained as 20 mM KMnO4 + 6.5% GO in 0.1 M phosphate buffer solution of pH 7. Under identical conditions, the MnOx-Pi-rGO catalyst exhibits 6.2 mA cm(-2) OER current against 2.9 mA cm(-2) by MnOx-Pi catalyst at 2.05 V in neutral phosphate solution. The Tafel slopes measured for OER at MnOx-Pi and MnOx-Pi-rGO are similar in magnitude at about 0.180 V decade(-1). The high Tafel slopes are attributed to partial dissolution of the catalyst during oxygen evolution. The O-2 evolved at the catalyst is measured by the water displacement method and the positive role of rGO on catalytic activity of MnOx-Pi is demonstrated.

Investigations into enhanced wax production with combustion synthesized Fischer-Tropsch catalysts

Combustion synthesized (CS) cobalt catalysts deposited over two supports, alumina and silica doped alumina (SDA), were characterized and tested for its Fischer-Tropsch (FT) activity. The properties of CS catalysts were compared to catalysts synthesized by conventional impregnation method (IWI). The CS catalysts resulted in 40-70% increase in the yield of C6+ hydrocarbons compared to MI catalysts. The FT activity for CS catalysts showed formation of long chain hydrocarbon waxes (C24+) compared to the formation of middle distillates (C-10-C-20) for IWI synthesized catalysts, indicating higher hydrocarbon chain growth probability for CS catalysts. This is ascribed to the smaller crystallite sizes, increased degree of cobalt reduction and consequentially, a higher number of active metal sites, exposed over the catalyst surface. Additionally, 12-13% increase in the overall C6+ hydrocarbon yield is realized for SDA-CS catalysts, compared to Al2O3-CS catalysts. The improved performance of CS-SDA catalysts is attributed to 48% increase in cobalt dispersion compared to Al2O3 supported CS catalysts, which is again caused by the decrease in the cobalt -support interaction for SDA supports. The metal support interactions were analyzed using XPS and H-2 TPR-TPD experiments. Combustion method produced catalysts with smaller crystallite size (17-18 nm), higher degree of reduction (similar to 92%) and higher metal dispersion (16.1%) compared to the IWI method. Despite its enhanced properties, the CS catalysts require prominently higher reduction temperatures (similar to 1100-1200 K). The hydrocarbon product analysis for Al2O3 supported catalyst showed higher paraffin wax concentrations compared to SDA supported catalysts, due to the lower surface basicity of Al2O3. This work reveals the impact of the CS catalysts and the nature of support on FT activity and hydrocarbon product spectrum. (C) 2016 Elsevier Ltd. All rights reserved.

Minuscule weight percent of graphene oxide and reduced graphene oxide modified Ag3PO4: new insight into improved photocatalytic activity

Designing and fabricating hybrid systems with a visible light active semiconductor as one of its components is an important research area for the development of highly efficient photocatalysts. Herein, we report visible-light driven photocatalytic activity of graphene oxide (GO) and controllably reduced GO (rGO) modified Ag3PO4 composites fabricated by an in situ method. Concentration of graphene derivatives in GO/rGO-Ag3PO4 composites was in the range of 0.13-0.52 wt% which is very minute compared to those reported previously. The optimal concentration of GO in Ag3PO4 with a kinetics (k = 1.23 +/- 0.04 min(-1)) for the degradation of rhodamine B is 0.26 wt%. GO-Ag3PO4 photocatalysts display an improved catalytic activity compared with pristine and rGOs modified Ag3PO4. In line with this, GO/rGO-Ag3PO4 composites show improved photocatalytic activity for the degradation of 2-chlorophenol compared with Degussa P-25. Our experiments with GO reduced to different extents show that, rGO with more polar functional groups exhibits a higher photocatalytic efficiency. The photocatalytic activity in the presence of different scavengers reveals that holes and O-2(-center dot) reactive species play major roles in the degradation phenomenon. In view of our experimental results and reported theoretical studies, a change in conduction band energy level and variation in the contribution of different charge orbitals (C 2p and O 2p) to the conduction band in the composite favours electron flow from graphene derivatives to the semiconductor, enhancing its photocatalytic response.

Analysis of Factors for Improving Functionality of Tin Oxide Gas Sensor

The proposed work discusses different parameters which are considered to improve the performance of a tin oxide-based thin film gas sensor. This includes analysing and deducing suitable catalytic additives to enhance the performance of the sensor in terms of selectivity and sensitivity. Chemical sensitization and electronic sensitization are performed to improve the rate of response of the sensor.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.