Enhancing charge transfer in a W18O49/g-C3N4 heterostructure via band structure engineering for effective SERS detection and flexible substrate applications

Abstract

Chemical mechanism (CM)-related surface-enhanced Raman spectroscopy (SERS) has received tremendous interest due to its exceptional stability and excellent uniformity. Nevertheless, there remains a demand for ingenious methodologies for promoting effective charge transfer (CT) to improve SERS sensitivity further. Herein, a band structure engineered W₁₈O₄₉/g-C₃N₄ heterostructure (WCN) was first employed as a CM-based SERS substrate with remarkable enhancement and sensitivity. To investigate the Raman enhancement properties of the substrate, malachite green (MG) was employed as the Raman probe with the excitation of a 633 nm laser. The WCN substrate exhibits a Raman enhancement factor (EF) of 2.6 × 10⁷, achieving a limit of detection (LOD) of 1.9 × 10⁻¹⁰ M for MG. The outstanding Raman amplification behavior can be attributed to the heterojunction-induced efficient CT process, energy band matching resonance due to minor doping with g-C₃N₄ serving as a band gap modifier, and improved photo-induced charge transfer (PICT) efficiency via the oxygen vacancies in the W₁₈O₄₉ units. Additionally, a flexible SERS substrate based on WCN was constructed using a vacuum filtration method and utilized to detect prohibited pharmaceutical residues on fish skin. The integration of this WCN and a nylon membrane not only preserves the Raman activity of the WCN for sensitive detection but also endows the Raman substrate with high flexibility and good mechanical durability, making it a potential candidate for in situ detection in particular environments.