ABSTRACT
The interlayer space of 2D materials can be a slit reactor where transformations not typical for the gas phase occur. We report redox reactions involving acetonitrile and nitrogen oxide guests in galleries of fluorinated graphite. Fluorinated graphite intercalation compounds with acetonitrile are treated with dinitrogen tetraoxide and the synthesis products are studied by a set of experimental methods. Data analysis reveals that N2O4 dissociates in fluorinated graphite matrices to form nitrogen-containing species NO3, NO2, NO, and N2. The interaction of NO3 with acetonitrile yields HNO3, which predominates as a guest in the synthesis products independently of the fluorination degree of the matrix. This reaction is accompanied by the removal of fluorine atoms weakly bonded to the graphite layers, leading to partial defluorination of the matrices. Our work demonstrates the possibility of using fluorinated graphite as a test nanoreactor whose dimension can be controlled by fluorination of the layers.
ABSTRACT
Tabby is a pattern of short irregular stripes, usually related to domestic cats. We have produced Tabby patterns on graphene by attaching fluorine atoms running as monoatomic chains in crystallographic directions. Separated by non-fluorinated sp 2 carbon ribbons, sp 3-hybridized carbon atoms bonded to zigzag fluorine chains produce sp 2-sp 3 interfaces and spin-polarized edge states localized on both sides of the chains. We have compared two kinds of fluorinated graphite samples C2F x , with x near to 1 and x substantially below 1. The magnetic susceptibility of C2F x (x < 1) shows a broad maximum and a thermally activated spin gap behaviour that can be understood in a two-leg spin ladder model with ferromagnetic legs and antiferromagnetic rungs; the spin gap constitutes about 450 K. Besides, stable room-temperature ferromagnetism is observed in C2F x (x < 1) samples: the crossover to a three-dimensional magnetic behaviour is due to the onset of interlayer interactions. Similarly prepared C2F x (x ≈ 1) samples demonstrate features of two-dimensional magnetism without signs of high-temperature magnetic ordering, but with transition to a superparamagnetic state below 40 K instead. The magnetism of the Tabby graphene is stable until 520 K, which is the temperature of the structural reconstruction of fluorinated graphite.
ABSTRACT
Development of graphene spintronic devices relies on transforming it into a material with a spin order. Attempts to make graphene magnetic by introducing zigzag edge states have failed due to energetically unstable structure of torn zigzag edges. Here, we report on the formation of nanoridges, i.e., stable crystallographically oriented fluorine monoatomic chains, and provide experimental evidence for strongly coupled magnetic states at the graphene-fluorographene interfaces. From the first principle calculations, the spins at the localized edge states are ferromagnetically ordered within each of the zigzag interface whereas the spin interaction across a nanoridge is antiferromagnetic. Magnetic susceptibility data agree with this physical picture and exhibit behaviour typical of quantum spin-ladder system with ferromagnetic legs and antiferromagnetic rungs. The exchange coupling constant along the rungs is measured to be 450 K. The coupling is strong enough to consider graphene with fluorine nanoridges as a candidate for a room temperature spintronics material.
