The reaction between fluorinated single-wall carbon nanotubes (F-SWNTs) and branched (M(w) = 600, 1800, 10000, and 25000 Da) or linear (M(w) = 25000 Da) polyethyleneimine (PEI) yields the covalent attachment of the polymer to the sidewalls of the nanotubes. The resulting PEI-functionalized SWNTs (PEI-SWNTs) were characterized by solid-state (13)C NMR, Raman spectroscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, atomic force microscopy, transmission electron microscopy, and thermal gravimetric analysis studies. As expected, the number of polymer molecules per SWNT is larger for low molecular weight PEI than for high molecular weight PEI. However, above 1800 Da, the number of polymer molecules per SWNT does not vary as much. This is supported by Raman spectral data that shows the D:G ratio is relatively insensitive of the molecular weight for M(w) > 1800 Da. The PEI-SWNTs are shown to have solubility in aqueous media of up to 0.4 mg x mL(-1). Solid-state (13)C NMR shows the presence of carboxylate substituents that have been attributed to carbamate formation as a consequence of the reversable CO(2) absorption to the primary amine substituents of the PEI. Desorption of CO(2) is accomplished by heating under argon at 75 degrees C, while the dependence of the quantity of CO(2) absorbed on temperature and the molecular weight of the PEI is reported. Under the conditions investigated the maximum absorption of 9.2% w/w is observed for PEI(25000)-SWNT at 27 degrees C. The possible CO(2) absorption applications of the PEI-SWNTs is discussed.

We demonstrate a high yield method of functionalizing graphene nanosheets through nitrene addition of azido-phenylalanine [Phe(N(3))] to exfoliated micro-crystalline graphite (microG). This method provides a direct route to highly functionalized graphene sheets. TEM analysis of the product shows few layer (n < 5) graphene sheets. The product was determined to have 1 phenylalanine substituent per 13 carbons.

Amine-based absorbents play a central role in CO2 sequestration and utilization. Amines react selectively with CO2, but a drawback is the unproductive weight of solvent or support in the absorbent. Efforts have focused on metal organic frameworks (MOFs) reaching extremely high CO2 capacity, but limited selectivity to N2 and CH4, and decreased uptake at higher temperatures. A desirable system would have selectivity (cf. amine) and high capacity (cf. MOF), but also increased adsorption at higher temperatures. Here, we demonstrate a proof-of-concept where polyethyleneimine (PEI) is converted to a high capacity and highly selective CO2 absorbent using buckminsterfullerene (C60) as a cross-linker. PEI-C60 (CO2 absorption of 0.14 g/g at 0.1 bar/90°C) is compared to one of the best MOFs, Mg-MOF-74 (0.06 g/g at 0.1 bar/90°C), and does not absorb any measurable amount of CH4 at 50 bar. Thus, PEI-C60 can perform better than MOFs in the sweetening of natural gas.

Abstract