ABSTRACT
Commercial titania photocatalysts were modified with silver nanoparticles (NPs) by the photodeposition method in the presence/absence of methanol. The obtained photocatalysts were characterized by XRD, XPS, diffuse reflectance spectroscopy, STEM, and time-resolved microwave conductivity (TRMC) methods. The photocatalytic activity was tested under UV/vis irradiation for (i) methanol dehydrogenation (during silver deposition), (ii) oxygen evolution with in situ silver deposition, and (iii) oxidative decomposition of acetic acid, as well as under vis irradiation for 2-propanol oxidation. The action spectra of 2-propanol oxidation were also performed. It has been confirmed that modification of titania with silver causes significant improvement of photocatalytic activity under both UV and vis irradiation as silver works as an electron scavenger (TRMC data) and vis activator (possibly by an energy transfer mechanism). The obtained activities differ between titania samples significantly, suggesting that the type of crystalline phase, particle/crystallite sizes, and electron traps' density are crucial for both the properties of formed silver deposits and resultant photocatalytic activity. It might be concluded that, under UV irradiation, (i) high crystallinity and large specific surface area are recommended for rutile- and anatase-rich samples, respectively, during hydrogen evolution, (ii) mixed crystalline phases cause a high rate of oxygen evolution from water, and (iii) anatase phase with fine silver NPs results in efficient decomposition of acetic acid, whereas under vis irradiation the aggregated silver NPs (broad localized surface plasmon resonance peak) on the rutile phase are promising for oxidation reactions.
ABSTRACT
Commercial titania photocatalysts were modified with silver and gold by photodeposition, and characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). It was found that silver co-existed in zero valent (core) and oxidized (shell) forms, whereas gold was mainly zero valent. The obtained noble metal-modified samples were examined with regard to antibacterial (Escherichia coli (E. coli)) and antifungal (Aspergillus niger (A. niger), Aspergillus melleus (A. melleus), Penicillium chrysogenum (P. chrysogenum), Candida albicans (C. albicans)) activity under visible-light irradiation and in the dark using disk diffusion, suspension, colony growth ("poisoned food") and sporulation methods. It was found that silver-modified titania, besides remarkably high antibacterial activity (inhibition of bacterial proliferation), could also decompose bacterial cells under visible-light irradiation, possibly due to an enhanced generation of reactive oxygen species and the intrinsic properties of silver. Gold-modified samples were almost inactive against bacteria in the dark, whereas significant bactericidal effect under visible-light irradiation suggested that the mechanism of bacteria inactivation was initiated by plasmonic excitation of titania by localized surface plasmon resonance of gold. The antifungal activity tests showed efficient suppression of mycelium growth by bare titania, and suppression of mycotoxin generation and sporulation by gold-modified titania. Although, the growth of fungi was hardly inhibited through disc diffusion (inhibition zones around discs), it indicates that gold does not penetrate into the media, and thus, a good stability of plasmonic photocatalysts has been confirmed. In summary, it was found that silver-modified titania showed superior antibacterial activity, whereas gold-modified samples were very active against fungi, suggesting that bimetallic photocatalysts containing both gold and silver should exhibit excellent antimicrobial properties.
