Redox reactions between acetonitrile and nitrogen dioxide in the interlayer space of fluorinated graphite matrices

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 N 2 O 4 dissociates in fluorinated graphite matrices to form nitrogen-containing species NO 3 , NO 2 , NO, and N 2 . The interaction of NO 3 with acetonitrile yields HNO 3 , 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. The insertion of N 2 O 4 into a fluorinated graphite matrix with acetonitrile initiates redox reactions in the interlayer space.