Combining the Potent Reducing Properties of Pecan Nutshell with a Solvent-Free Mechanochemical Approach for Synthesizing High Ag⁰ Content-Silver Nanoparticles: An Eco-Friendly Route to an Efficient Multifunctional Photocatalytic, Antibacterial, and Antioxidant Material

Abstract

A straightforward, low-cost, and scalable solid-state mechanochemical protocol for the synthesis of silver nanoparticles (AgNP) based on the use of the highly reducing agri-food by-product pecan nutshell (PNS) is reported herein. Under optimized conditions (180 min, 800 rpm, PNS/AgNO3 ratio = 55/45 w/w), a complete reduction in silver ions was achieved, leading to a material containing ca. 36% w/w Ag0 (X-ray diffraction analysis). Dynamic light scattering and microscopic analysis showed a uniform size distribution (15–35 nm average diameter) of the spherical AgNP. The 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assay revealed lower—although still absolutely high (EC50 = 5.8 ± 0.5 mg/mL)—antioxidant properties for PNS for the further incorporation of AgNP, supporting the efficient reduction of Ag+ ions by PNS phenolic compounds. Photocatalytic experiments indicated that AgNP-PNS (0.4 mg/mL) was able to induce the >90% degradation of methylene blue after 120 min visible light irradiation, with good recycling stability. Finally, AgNP-PNS demonstrated high biocompatibility and significantly light-enhanced growth inhibition properties against Pseudomonas aeruginosa and Streptococcus mutans at concentrations as low as 250 μg/mL, also eliciting an antibiofilm effect at 1000 μg/mL. Overall, the adopted approach allowed to reuse a cheap and abundant agri-food by-product and required no toxic or noxious chemicals, making AgNP-PNS a sustainable and easy-to-access multifunctional material.

Keywords

• silver nanoparticles
• green chemistry
• mechanochemistry
• waste valorization
• condensed tannins