Estimation of the surface interaction mechanism of ZnO nanoparticles modified with organosilane groups by Raman Spectroscopy

• Published in: Ceramics international Vol. 43; no. 15; pp. 11838 - 11847
• Main Authors: Jaramillo, A.F., Baez-Cruz, R., Montoya, L.F., Medinam, C., Pérez-Tijerina, E., Salazar, F., Rojas, D., Melendrez, M.F.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 15.10.2017
• Subjects: APTES; Functionalization; Raman Spectroscopy; ZnO Nanoparticles; Raman Spectroscopy; ZnO Nanoparticles; APTES; Functionalization
• ISSN: 0272-8842; 1873-3956
• DOI: 10.1016/j.ceramint.2017.06.027

We investigated the surface modification of zinc oxide nanoparticles (ZnO-NPs) with 3-aminopropyltriethoxysilane (APTES). The ZnO-NPs were synthesized by the physical method of continuous arc discharge in controlled atmosphere (DARC-AC). The surface modification was performed using a chemical method with constant stirring and reflux for 24h at room temperature. This surface functionalization of the ZnO nanoparticles (funct-ZnO-NPs) was experimentally confirmed by infrared spectroscopy (FT-IR), Raman spectroscopy, TGA, UV–Visible and XRD, while its morphological characterization was performed by HRTEM. Using Raman spectroscopy, it was possible to study the functionalization process after the change, as well as the appearance of new bands of the molecular vibrations produced by the chemical interaction of the surface of the nanoparticles with the silane coupling agent. Comparing the Raman spectra of the ZnO-NPs, APTES and funct-ZnO-NPs, it was observed that the area between 2700 and 3200cm−1 related to the vibrations of the CH2 and CH3 bonds of the APTES molecule. The funct-ZnO-NPs showed a decrease in the peak intensity, which indicates a deactivation of the degrees of freedom of the APTES at the time of the surface functionalization with the ZnO-NPs, suggesting a redistribution of the APTES CH2 groups, as they interact with the surface of the ZnO-NPs. The APTES molecule is anchored to the surface of the ZnO-NPs via one or two Si-O-Zn bonds and not by three, as is commonly reported. The above finding is attributable to steric impediment of the side groups of the APTES and the strain of the Si-O-Zn bonds that hinders the trivalent interaction with the surface of the nanostructured ZnO. Similarly, the results obtained by Raman were verified and complemented by means of FT-IR due to the presence of bands at specific wavelengths.