Porous pillared graphene oxide (GO) materials were prepared using solvothermal reaction of Hummers GO with solution of Tetrakis(4-aminophenyl)methane (TKAm) in methanol. The intercalation of TKAm molecules between individual GO sheets, performed under swelling condition, results in expansion of inter-layer distance of GO from ~7.5 Å to 13-14 Å. Pillaring GO with bulky, rigid 3D shaped TKAm molecules could be an advantage for the preparation of stable pillared structures compared to e.g. aliphatic or aromatic diamines. Insertion of TKAm molecules into inter-layer space of GO results in formation of interconnected network of sub-nanometer slit pores. The expanded GO structure prepared with optimized GO/TKAm composition shows Specific Surface Area (SSA) up to 660 m2/g which is among the highest reported for GO materials pillared using organic spacers. Modelling of GO structures pillared with TKAm molecules shows that maximal SSA of about 2300 m2/g is theoretically possible for realistic concentration of pillaring molecules in GO interlayers. Hydrogen sorption by pillared GO/TKAm is found to follow standard correlation with SSA both at ambient and liquid nitrogen temperatures with highest\ud
uptakes of 1.66 wt% achieved at 77 K and 0.25 wt% at 295 K. Our theoretical simulations show that pillared GO structures do not provide improvement of hydrogen storage beyond well-established physisorption trends even for idealized materials with subnanometer pores and SSA of 2300 - 3700 m2/g
The selective functionalization of carbon nanotube surfaces is crucial for many potential applications of these materials. For this purpose several oxidants, among other substances, are used. The aim is to reach a large degree of functionalization which depends on the oxidant character of the reagent. For this reason the functionalization of multiwall carbon nanotubes (MWCNTs) by treatment with ozone in basic solution is studied. At basic pHs, ozone results into hydroxyl radicals whose reduction potential is very high (E°= 3.06 V). The results have been compared to those obtained by ozone in gas phase and with cold oxygen plasma. The oxidation with ozone in basic solution seems to be kinetically restricted. As a consequence, the degree of oxidation in this medium is smaller than this of ozone gas, in spite of the larger oxidation capacity of the former. The oxygen-containing groups fixed by these two treatments are mainly attached to defects of the nanotubes. Moreover, no modification of the graphene layers and no porosity result from these treatments. The oxygen plasma treatment stands out in the content of oxygen groups fixed to the MWCNTs, as it is by far more effective, although some of these groups have relatively low thermal stability. Nevertheless, this treatment mainly fixes the oxygen groups on the walls of the nanotubes.
Synthetic polyammonium/polyamine receptors are known to enhance ATP dephosphorylation in solution. ATP interaction with a G-3 poly(ethylene imine) dendrimer shows an unprecedented behaviour, the dendrimer catalyst being able to enhance or inhibit dephosphorylation of the nucleotide depending on the solution pH.
Controlling the chemistry on the surface of new carbon materials is a key factor to widen the range of their applicability. In this paper we show a grafting methodology of polyalkylamines to the surface of carbon nanomaterials, in particular, carbon nanotubes and a carbon black. The aim of this work is to reach large degrees of covalent functionalization with hyperbranched polyethyleneimines (HBPEIs) and to efficiently preserve the strong chelating properties of the HBPEIs when they are fixed to the surface of these carbon materials. This functionalization opens new possibilities of using these carbon nanotubes-based hybrids. The results show that the HBPEIs are covalently attached to the carbon materials, forming hybrids. These hybrids emerge from the reaction of amine functions of the HBPEIs with carbonyls and carboxylic anhydrides of the carbon surface which become imine and imide bonds. Thus, due to the nature of these bonds, the pre-oxidized samples with relevant number of C=O groups showed an increase in the degree of functionalization with the HBPEIs. Furthermore, both the acid-base properties and the coordination capacity for metal ions of the hybrids are equivalent to that of the free HBPEIs in solution. This means that the chemical characteristics of the HBPEIs have been efficiently transferred to the hybrids. To reach this conclusion we have developed a novel procedure to assess the acid-base and the coordination properties of the hybrids (solids) by means of potentiometric titration. The good agreement of the values obtained for the hybrids and for the free HBPEIs in aqueous solution supports the reliability of the procedure. Moreover, the high capacity of the hybrids to capture Ni2+ by complexation opens new possibilities of using these hybrids to capture high-value metal ions such as Pd2+ and Pt2+.
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