▎ 摘　　要

The intimate interplay of chitosan (CS) and graphene oxide (GO) in aqueous acidic solution has been explored to design upon casting, nanostructured "brick-and-mortar" films (CS-GO-f) and by acidic to -basic pH inversion, porous CO2-dried aerogel microspheres (CS-GO-m). Owing to the presence of oxygenated functional groups in GO, good-quality crack-free hybrid films were obtained. Mechanical properties were improved independently of the GO content and it was found that a 20 wt% loading affords hybrid film characterized with a Young modulus three times superior to that reached with the same loading of layered clay. The presence of graphene oxide was found to be detrimental for the thermal stability of the polysaccharide at T <350 degrees C, a fact attributed to the well-established decomposition of the oxygenated functional groups of the graphene sheets. Irrespective to the graphene oxide loading, chitosan-graphene oxide mixture preserves the gelation memory of the polysaccharide. Supercritical drying of the resulting soft hydrogels provides macroporous network with surface areas ranging from 226 m(2) g(-1) to 554 m(2) g(-1). XPS and RAMAN analyses evidenced the selective reduction of GO sheets inside of these microspheres, affording the hitherto unknown macroporous chitosan-entangled-reduced graphene oxide (CS-rGO-m) aerogels. Improvement in both hydrothermal stability (under water reflux) and chemical stability (under acidic conditions) have been noticed for chitosan-graphene oxide microspheres with respect to non modified chitosan and chitosan-clay bio-hybrids, a result rooted in the substantial hydrophobic character imparted by the addition of graphenic material to the polysaccharide skeleton. In essence, this contribution demonstrates that graphene oxide loading do not disturb neither the filmogenicity of chitosan nor its gelation ability and constitutes a promising route for novel chitosan-based functional hybrid materials. (C) 2017 Elsevier Ltd. All rights reserved.