Preparation and Characterisation of a Halloysite Nanoclay–Anthocyanin Hybrid Under Variable Conditions

The development of sustainable pigments from natural sources is gaining interest due to environmental concerns and the need for bio-based alternatives to synthetic dyes. This study investigates the synthesis of hybrid pigments by adsorbing anthocyanins—extracted from pomegranate agro-waste—onto halloysite (HA) nanotubes. A full factorial design was applied to evaluate the influence of pH and surfactant type (cetylpyridinium bromide and sodium dodecyl sulfate) on pigment colour and the thermal and structural stability of the hybrids. Adsorption was carried out in 400 mL dispersion baths containing 10 g of HA and 5% w/w anthocyanins. Surfactants (2% w/w) were added before the pigment, followed by 200 µL of silane. Dispersions were stirred at high speed for 1 h and then at 500 rpm for 23 h to ensure adsorption without premature desorption. Characterisation (TGA, XRD, FTIR, UV-Vis/NIR, SEM, EDX, BET) confirmed the preservation of HA structure and minimal changes in thermal behaviour. Pigment colour varied with synthesis conditions, especially pH: a higher pH increased brightness and yielded yellowish tones, while a lower pH resulted in reddish-blue hues with greater variability. The results confirm halloysite’s potential as a stable carrier for natural dyes and demonstrate that pH effectively tunes hybrid pigment colour.