⿢The modified-MWNTs show enhanced ORR activities both in acidic and alkaline media.⿢The modified-MWNTs exhibit a superior long-time stability and tolerance.⿢A deprotonated state of carboxyl groups in alkaline is proved by experiments.⿢Carboxyl groups play a crucial role in determining the ORR activity of MWNTs.⿢The ORR mechanisms of functional groups are revealed by theoretical calculations.Functionalization of carbon nanotubes (CNTs) has been proven to be an effective method to modulate their properties including electrocatalytic activity. Here, we report the catalytic properties of CNTs modified with various functional groups in the oxygen reduction reaction (ORR). Experimental data show that ORR activity of CNTs is enhanced markedly with increasing content of carboxyl groups, and MWNT-COOH sample display the highest current density and most positive onset potential among the studied catalysts. Remarkably, the functionalized CNTs exhibit excellent long-time stability and tolerance towards alcohols. Both experimental and theoretical results suggest that the deprotonated state of carboxyl groups promote the ORR electrocatalytic performance of CNTs in an alkaline electrolyte.Download high-res image (285KB)Download full-size image

The mechanism of SO2 capture by 1-(2-diethylaminoethyl)-3-methylimidazolium tetrazolate ([Et2NEMim][Tetz]) was investigated using B3LYP hybrid density functional methods at 6-31 + G(d,p) level. In order to find the origin of the high capacity of the subjected ionic liquids (IL) for SO2 capture, the 1: n (n = 1–5) complexes formed between [Et2NEMim][Tetz] and 1–5 SO2 molecules were optimized. Two interaction modes (π-hole interaction and hydrogen bond) were found in each 1: n (n = 1–5) complex; the second order perturbation stabilization energies, E(2)s, confirmed that the main interaction mode was a π-hole interaction. The calculated interaction energies indicated that the first SO2 absorption should be chemical absorption. The capture of the second and third SO2 should fall between chemical and physical interaction, and the fourth and fifth SO2 are incorporated by physical absorption. Thermodynamic analyses indicated that SO2 capture favors lower temperature and higher pressure. Owing to the interactions between SO2 and the [Tetz] anion or the [Et2NEMim] cation, the SOO asymmetric stretching frequency exhibits an obviously red shift in the complex. The strong absorptions of SOO asymmetric stretching in complex (1:5) appear at 1295 cm−1 (interaction between SO2 and the [Tetz]− anion) and 1247 cm−1 (interaction between SO2 and the tertiary nitrogen on the cation).

Carbon modified lithium titanate (Li4Ti5O12) anode nanocrystals for Li-ion batteries were synthesized by directly treating the titanium alkoxide and lithium acetate ethanol solution via the Reaction under Autogenic Pressure at Elevated Temperature (abbreviated to RAPET). The mixture of the liquid precursors decomposed during the RAPET process and then reacted in situ and transformed into carbon-modified Li4Ti5O12 anode nanocrystals. The organic moieties in the titanium alkoxide and the lithium salt provided both the oxygen and carbon for the synthesis. The resulting products were characterized by X-ray diffraction (XRD), elemental analysis, scanning electronic microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), nitrogen adsorption–desorption measurements, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge testing. The influences of the titanium alkoxide precursors, i.e. the length of the alkoxy group, on the properties of the final products and the presence of the in situ resulting carbon on the electrochemical performance have been investigated.

The chemo-, diastereo-, and enantioselectivities in proline and axially chiral amino sulfonamide-catalyzed direct aldol reactions between two enolizable aldehydes with different electronic nature have been studied with the aid of density functional theory (DFT) method. The potential energy profiles for the enamine formation between each aliphatic aldehyde and the catalyst confirm that two subject catalysts can successfully differentiate between 3-methylbutanal as an enamine component and α-chloroaldehydes as a carbonyl component. Transition states associated with the stereochemistry-determining C–C bond-forming step with the enamine intermediate addition to the aldehyde acceptor for proline and chiral amino sulfonamide-promoted aldol reactions are reported. DFT calculations not only provide a good explanation for the formation of the sole cross-aldol product between two aliphatic aldehydes both bearing α-methylene protons but also well reproduce the opposite syn vs anti diastereoselectivities in the chiral amino sulfonamide and proline-catalyzed aldol reactions.