Surface Modification of Lignite with Alkyl and Mixed Alkyl‐Aryl Films Generated from an Aryl Diazonium Salt and Alkyl Halides: Experimental Results and Theoretical Analyses

The surface of lignite has been modified with alkylcarboxylic moieties derived from alkyl halides by diverting the reactivity of the sterically hindered aryl radical obtained by reduction of the 2,6-dimethylbenzene diazonium tetrafluoroborate after its chemical reduction. Mixed alkyl-aryl layers are prepared by using 4-nitro or 3,5-bis-trifluoro benzenediazonium salts.

Abstract

In search of new possible uses of cheap lignite from the Kosova Bassin, the surface of lignite powders is modified with alkyl or mixed alkyl-aryl layers. Modification is performed in aqueous acid solution containing an aryl diazonium salt and an alkyl halide compound in millimolar concentration, in the presence of potassium iodide as a reducing agent at equimolar concentration. Attachment of alkyl films substituted with carboxylic groups and aryl films with nitro or bis-trifluoromethyl groups is characterized by IRATR and XPS spectroscopy. The formation of a stable interface during the grafting reactions of alkyl and aryl moieties with lignite surface has been confirmed by theoretical calculations. Aryl diazonium salts once chemically or spontaneously reduced are a source of aryl radicals, able to attach chemically to the material surface or to react with alkyl halides by abstracting the halogen atom. If the aryl diazonium salts are unable to graft to the coal surface due to steric hindrance, they can, nevertheless, abstract an iodine or bromine atom to generate alkyl radicals that react with the material surface.

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