Improved charge-transfer resonance in graphene oxide/ZrO2 substrates for plasmonic-free SERS determination of methyl parathion

Abstract

This work reports a sensitive SERS substrate based on graphene oxide (GO) and quantum-sized ZrO₂ nanoparticles (GO/ZrO₂) for label-free determination of the organophosphate pesticide methyl parathion (MP). The enhanced light-matter interactions and the consequent SERS effect in these substrates resulted from the effective charge transfer (CT) mechanism attributed to synergistic contributions of three main factors: i) the strong molecular adherence of the MP molecules and the ZrO₂ surface which allows the first layer-effect, ii) the relatively abundant surface defects in low dimensional ZrO₂ semiconductor NPs, which act as intermediate electronic states that reduce the large bandgap barrier, and iii) the hindered charge recombination derived from the transference of the photoinduced holes to the GO layer. This mechanism allowed an enhancement factor of 8.78 × 10⁴ for GO/ZrO₂-based substrates, which is more than 5-fold higher than the enhancement observed for platforms without GO. A detection limit of 0.12 μM was achieved with an outstanding repeatability (variation ≤4.5%) and a linear range up to 10 μM, which is sensitive enough to determine the maximal MP concentration permissible in drinking water according to international regulations. Furthermore, recovery rates between 97.4 and 102.1% were determined in irrigation water runoffs, strawberry and black tea extracts, demonstrating the reliability of the hybrid GO/ZrO₂ substrate for the organophosphate pesticides quantification in samples related to agri-food sectors and environmental monitoring.

Keywords: Charge-transfer mechanism; Chemical enhancement; Environmental monitoring; Plasmonic-free analysis; Semiconductor SERS; Water analysis.