Utilizing Freeze-Thaw-Ultrasonication to Prepare Mesoporous Silica-Encapsulated Colloidal Silver Nanoaggregates with Long-Term Surface-Enhanced Raman Spectroscopy Activity

Surface-enhanced Raman spectroscopy (SERS) is widely employed due to its high sensitivity and distinctive fingerprinting capabilities. Colloidal nanoaggregates are commonly used as SERS substrates because of their mobility and the abundance of "hotspots". Although the reagent-free "freeze-thaw-ultrasonication" method for preparing Ag nanoaggregates (AgNAs) does not introduce additional background interference and maintains the original interfacial properties of AgNAs, their unstable physical nanostructure limits SERS detection to just 7 days. Herein, we demonstrate mesoporous silica-encapsulated colloidal Ag nanoaggregates (AgNAs@m-SiO₂) by combining a freeze-thaw-ultrasonication method and a cetyltrimethylammonium bromide (CTAB)-assisted silanization reaction, achieving long-term SERS stability of more than two months. The prepared AgNAs@m-SiO₂ serve a dual capability: (1) preserving electromagnetic "hotspots" for ultra-sensitive detection (e.g., malachite green detection limit: 3.60 × 10^-⁸ M), and (2) maintaining structural stability under harsh conditions. The AgNAs@m-SiO₂ substrate exhibited superior structural stability after 50 min of ultrasonic treatment, with an initial SERS signal retention of 91.8%, which is twice that of the bare AgNAs (retention of 45%). The long-term performance further highlighted its superiority: after 70 days of storage, the composite maintained 84.3% of its original signal strength, outperforming the uncoated controls by over ten times (which retained only 8%). Crucially, the substrate's robust design enables the direct detection of contaminants in real environmental matrices (river and seawater) for qualitative analyses and water quality assessments, thus validating its suitability for environmental sensing applications in the field.