Nickel foam–caged Ag-Au bimetallic nanostructure as a highly rugged and durable SERS substrate

Abstract

A three-dimensional nickel foam (NF) caging Ag-Au bimetallic nanostructure (Ag-Au@NF) has been demonstrated as a highly rugged and sensitive surface-enhanced Raman scattering (SERS) substrate. The main concept employed in designing this substrate was the protection of SERS-active nanostructures by holding them within a sturdy frame. For this purpose, NF was readily chosen as a strong porous frame to secure the internal nanostructures owing to its excellent structural strength and ability to easily incorporate analytes due to its porous structure. The next issue was the construction of stable and SERS-efficient nanostructures within the NF frame. To meet this need, an Ag-Au bimetallic nanostructure was chosen, combining the high SERS efficiency of Ag and the good surface stability of Au. To fabricate the Ag-Au nanostructure, first a Sn-Ag alloy was constructed on the NF frame by means of electrodeposition (producing Sn-Ag@NF) and then Sn was selectively leached from the alloy by means of free corrosion in NaOH solution (producing Ag@NF). This selective leaching was adopted to make the surface rough to enhance the SERS efficiency in the final substrate. Finally, Au was incorporated into the Ag@NF by means of a galvanic replacement reaction (producing Ag-Au@NF). The use of Ag-Au@NF enabled identification of rhodamine 6G at concentrations as low as 0.1 nM. The Ag-Au@NF substrates were rugged, showing small Raman signal drops after 100 cycles of sandpaper abrasion or 30 min of sonication. Also, the signal decrease was only 4.26% upon 3 days of exposure to ambient air without special care. Overall, the Ag-Au@NF developed herein shows practical merits for adoption in routine and field SERS analyses.