Teng Chen

Graphene-based porous materials with tunable surface area and CO2 adsorption properties synthesized by fluorine displacement reaction with various diamines.

A mild, operationally simple and controllable protocol for preparing graphene-based porous materials is essential to achieve a good pore-design development. In this paper, graphene-based porous materials with tunable surface area were constructed by the intercalation of fluorinated graphene (FG) based on the reaction of reactive CF bonds attached to graphene sheets with various amine-terminated molecules. In the porous materials, graphene sheets are like building blocks, and the diamines covalently grafted onto graphene framework act as pillars. Various diamines are successfully grafted onto graphene sheets, but the grafting ratio of diamines and reduction degree of FG differ greatly and depend on the chemical reactivity of diamines. Pillared diamine molecules chemically anchor at one end and are capable of undergoing a different reaction on the other end, resulting in three different conformations of graphene derivatives. Nitrogen sorption isotherms revealed that the surface area and pore distribution of the obtained porous materials depend heavily on the size and structure of diamine pillars. CO2 uptake capacity characterization showed that ethylenediamine intercalated FG achieved a high CO2 uptake density of 18.0 CO2 molecules per nm(2) at 0°C and 1.1bars, and high adsorption heat, up to 46.1kJmol(-1) at zero coverage.

Various surface functionalizations of ultra-high-molecular-weight polyethylene based on fluorine-activation behavior

Ultra-high-molecular-weight-polyethylene (UHMWPE) is an excellent biological material, but covalently introducing a variety of functional groups on its surface is very difficult owing to its inherently inert structure. In this study, the surface functionalization of UHMWPE based on fluorine-activation and subsequent derivatization reactions is reported, and offers a simple and convenient pathway to the incorporation of useful functional groups and patterned surface functionality. A large number of carboxyl groups, –C–Fx and CC bonds are covalently bonded to the macromolecular chain structure through a fluorine-activated process in the presence of oxygen, greatly increasing the surface polarity and wettability. Its surface energy is increased from 34.5 mN m−1 to 57.5 mN m−1, and the polar component arises from 4.0 to 23.8 mN m−1. In contrast, only stable C–F forms when treated with only fluorine (no oxygen), producing a hydrophobic Teflon-like surface structure and poor wettability. Moreover, UHMWPE with carboxyl groups and double bonds, used as precursor, were further covalently functionalized through subsequent derivatization reactions with fluorine, bromine and amine-terminated molecules, by which the carbon–bromine bond and amino groups were successfully grafted onto a UHWMPE surface. The results demonstrate that the fluorine-activated strategy developed in this work is an effective means to improve the surface hydrophilicity and derivatization reaction capacity of UHMWPE.

The reaction kinetics and mechanism of crude fluoroelastomer vulcanized by direct fluorination with fluorine/nitrogen gas

A novel vulcanization method for crude fluoroelastomer by direct fluorination with fluorine/nitrogen gas has been investigated. The results show that the vulcanization reaction of fluoroelastomer is closely related with fluorination temperature, fluorination time and fluorine gas partial pressure. The maximum crosslink degree can be up to 97%, and the fluorine content of fluoroelastomer increased from 48.2% to 60% during the fluorination. The static friction coefficient of fluoroelastomer is decreased from 0.91 to 0.55, which is about 39.6% reduction after fluorination. The ATR-FTIR spectra indicate the crosslink reaction process of fluoroelastomer by direct fluorination, which arises from three reaction stages and successively goes through four elementary reactions: substitution reaction; elimination reaction; addition reaction; crosslink reaction. The increase of fluorine content takes place mainly in the first stage, and the crosslink reaction takes place mainly in the second stage and third stage.