Investigation of Sulfur Doping in Mn-Co Oxide Nanotubes on Surface-Enhanced Raman Scattering Properties

Doping engineering is an efficient strategy to manipulate the optoelectronic properties of metal oxides for sensing, catalysis, and energy applications. Herein, we have demonstrated the fabrication of sulfur (S)-doped Mn-Co oxides to regulate their band and surface electronic structures, which is beneficial to enhancing the charge transfer (CT) between the metal oxides and their adsorbed molecules. As expected, significantly enhanced SERS signals are achieved on S-doped Mn-Co oxide nanotubes, and the minimum detection concentration can reach as low as 10^-8 M. Furthermore, the change in the electronic structure caused by S-doping provides different microelectric fields to influence the orientation of the interaction between the probe molecules and the substrate. Additionally, the evaluation of the oxidase-like catalytic activity of the substrate proved that, with an increase in the ratio of Co²⁺/Co³⁺ content, the number of electrons on the substrate increases, which promotes the CT process and further increases the degree of CT. The nonmetallic doping route in semiconducting metal oxides can provide effective and stable SERS activity; moreover, it provides a new strategy for exploring the relationship between CT in catalysis and SERS performance of semiconductors.