Solvent-free mechanochemical mild oxidation method to enhance adsorption properties of chitosan

Abstract

• Solvent-free chitosan oxidation is obtained by rapid mechanochemical reaction.

• Different oxidants induce very diverse physicochemical changes on chitosan.

• Oxidized chitosan with persulfate or percarbonate has improved adsorption capacity.

• Uptake on oxidized chitosan with persulfate is 125-fold faster than on pristine one.

Oxidation has been profitably utilized to improve some properties of chitosan. However, only solvent-based oxidation procedures have been proposed so far, which are hardly feasible at industrial scale in an economic way because of product recovery cost. In this study, a solvent-free, rapid, and effective oxidation method is proposed. It is based on direct solid-state reaction between chitosan and oxidant powder in a mechanochemical reactor. Results prove that by short high energy ball milling (<3 h) it is possible to achieve diverse physicochemical modifications employing different reagents. Apart from polysaccharidic chain shortening, persulfate provokes high amorphization and induces formation of ketonic groups; percarbonate heightens deacetylation degree, preserving in part crystallinity; calcium peroxide merely deprotonates amino groups and increases amorphization degree. Adsorption tests with the azo-dye reactive red 2 show that adsorption capacity of chitosan co-milled with persulfate (974 mg/g milled product), which is the best performing adsorbent, is twice that of pristine chitosan, while adsorption rate is outstandingly boosted (125 times).

Graphical abstract

Keywords

Chitosan / High energy ball milling / Mechanochemistry / Oxidation

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