Surface‐Engineered Hydrophobic Porous Organic Polymer for Enhanced SERS Detection of Plasticizers

Abstract Surface‐enhanced Raman spectroscopy (SERS) has emerged as a powerful analytical tool for the detection of plasticizers, offering ultrasensitive fingerprint recognition, convenient operation, and minimal interference from water. Herein, a gold‐anchored and thiol‐functionalized superhydrophobic porous organic polymer (Au@POP‐SH) for the rapid, sensitive, and selective detection of Phthalic acid esters (PAEs) is developed. Au@POP‐SH is synthesized from POP‐OH using N,N ‐dimethyl(thiocarbonyl) chloride under solvothermal conditions, enabling the anchoring of gold nanoparticles onto thiol groups with significant textural parameters. The resultant Au@POP‐SH efficiently detects a broad range of phthalic acid esters demonstrating remarkable sensitivity with a lowest detectable concentration of 7.33 × 10 −13 m for dibutyl phthalate (DBP) through SERS. It should be noted that Au@POP‐SH exhibited excellent stability and a rapid, highly sensitive, and specific approach for SERS‐based phthalic acid ester detection arises from the synergy between AuNPs and POP‐SH, enabling hot spots, analyte adsorption and π–π interactions. Furthermore, advanced density functional theory (DFT) calculations reveal the interaction mechanism between Au@POP‐SH and phthalic acid esters, enabling selective detection of dimethyl phthalate (DMP) and DBP. Multivariate analysis with spectral preprocessing improves SERS quantification, and partial least squares models show strong correlation (R² = 0.9992) confirming that SERS combined with chemometric methods offers a robust analytical strategy for plasticizer detection.