Synthesis, Photocatalytic, and Antifungal Properties of MgO, ZnO and Zn/Mg Oxide Nanoparticles for the Protection of Calcareous Stone Heritage

More recently, the biological colonization of stone heritage and consequently its biodeterioration has become the focus of numerous studies. Among all microorganisms, fungi are considered to be one of the most important colonizers and biodegraders on stone materials. This is why the development of new antifungal materials requires immediate action. ZnMgO nanoparticles (NPs) have several exciting applications in different areas, highlighting as an efficient antimicrobial agent for medical application. In this research, the application of Zn-doped MgO (Mg1–xZnxO, x = 0.096) NPs obtained by sol–gel method as antifungal coatings on dolomitic and calcitic stones has been explored as a means to develop effective protective coatings for stone heritage. Moreover, the photocatalytic and antifungal activity of Mg1–xZnxO NPs were comparatively studied with single ZnO and MgO NPs. Thus, compared to the MgO and ZnO nanomaterials, the Mg1–xZnxO NPs exhibited an enhanced photocatalytic activity. After UV irradiation for 60 min, 87% methylene blue was degraded over Zn-doped MgO NPs, whereas only 58% and 38% of MB was degraded over ZnO and MgO NPs, respectively. These nanoparticles also displayed a better antifungal activity than that of single pure MgO or ZnO NPs, inhibiting the growth of fungi Aspergillus niger, Penicillium oxalicum, Paraconiothyrium sp., and Pestalotiopsis maculans, which are especially active in the bioweathering of stone. The improved photocatalytic and antifungal properties detected in the Mg1–xZnxO NPs was attributed to the formation of crystal defects by the incorporation of Zn into MgO. The application of the MgO- and Zn-doped MgO NPs as protective coatings on calcareous stones showed important antifungal properties, inhibiting successfully the epilithic and endolithic colonization of A. niger and P. oxalicum in both lithotypes, and indicating a greater antifungal effectiveness on Zn-doped MgO NPs. The use of Zn-doped MgO NPs may thus represent a highly efficient antifungal protection for calcareous stone heritage.
This research has been financially supported under projects FOMIX-Yuc 2008–108160, CONACYT LAB-2009-01-123913, 188345, Fronteras de la Ciencia No. 138, by the Community of Madrid under the Geomaterials 2 Programme (S2013/MIT_2914), Climortec, BIA2014–53911-R and MAT2013-47460-C5-5-P, and the Autonomous Region Program of Madrid, MULTIMAT CHALLENGE (S2013/MIT-2862). A.S.-F. would like to gratefully acknowledge the financial support of Santander Universidades through “Becas Iberoamérica Jóvenes Profesores e Investigadores, España 2015” scholarship program.