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

Highlights

• 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.

Abstract

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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Acknowledgements

This study was financially supported by the Major Science and Technology Program for Water Pollution Control and Treatment in China (No. 2017ZX07202003) and the National Key Research and Development Program of China (No. 2018YFC1803100).

Electronic Supplementary Material

ƒSupplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-021-1416-4 and is accessible for authorized users.

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