Spatially Confined Radical Addition Reaction for Electrochemical Synthesis of Carboxylated Graphene and its Applications in Water Desalination and Splitting.

Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (●COOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined ●COOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.

Photoinduced Atom Transfer Radical Addition Reaction of Olefins with α-Bromo Carbonyls.

The irradiation of halogen-bonded complexes with light leads to the homolysis of carbon-halogen bonds and the formation of the corresponding carbon radical species. However, the only methodology reported for these halogen-bonding complexes is using CBr4 as the halogen-bond donor and its applicability is of great interest. In this study, the atom transfer radical addition (ATRA) reaction of olefins using bromomalonates as halogen-bonding donors was developed. Using 4-phenylpyridine as the halogen-bonding acceptor, the desired reaction proceeded well under external irradiation of 380 nm light to furnish the corresponding ATRA reaction product. The ATRA reaction was effective in generating the corresponding products for a variety of olefins. Furthermore, the ATRA reaction was applicable to bulky ketones, substrates, and malonate esters. The intermediates of the reaction were identified and a plausible reaction mechanism was proposed.

Mechanism and kinetics of diuron oxidation by hydroxyl radical addition reaction.

Diuron is a phenyl urea herbicide used to control weeds in agricultural lands. The degradation of diuron in the atmosphere takes place dominantly via reaction with OH radicals. In this work, the OH addition reaction of diuron has been studied by using density functional theory methods M06-2X, ωB97X-D and MPWB1K with 6-31G(d,p) basis set. The calculated thermochemical parameters show that OH addition reaction occurs favourably at C2 position of diuron. The rate constant is calculated for the favourable initial reaction pathway by using canonical variational transition state theory with small curvature tunnelling (SCT) correction over the temperature range of 200-1000 K. The reaction of initially formed diuron-OH adduct intermediate with O2 leads to the formation of peroxy radical intermediate. The reaction of peroxy radical intermediate with HO2 and NOx (x = 1, 2) radicals is studied in detail. The results obtained from time-dependent density functional theory (TDDFT) calculations show that the intermediates and products formed from oxidation of diuron can be easily photolyzed in the sunlight. This study provides thermodynamical and kinetic data for the atmospheric oxidation of diuron by OH radical addition reaction and demonstrates the atmospheric chemistry of diuron and its derivatives.