Degradation of p-nitrophenol and bacteria with TiO2 xerogels sensitized in situ with tetra(4-carboxyphenyl)porphyrins

Heterogeneous photocatalysis is widely studied for environmental applications as oxidative processes can completely destroy organic pollutants such as alkanes, pesticides, dyes, etc. and microorganisms. The most used photocatalyst is the commercial TiO2 Degussa P25, which is composed of 80% anatase and 20% rutile and which is active when TiO2 is exposed to UV light ( < 380 nm). Recently, several studies have been performed to extend the light absorption range of TiO2 towards the visible range.
In this study, TiO2-based materials doped with porphyrins, a widely used dye for the photosensibilization of TiO2, have been prepared using a sol-gel process. To stabilize the TiO2-dye interactions, free metal tetra(4-carboxyphenyl)porphyrin and nickel tetra(4-carboxyphenyl)porphyrin were introduced in situ into the TiO2 matrix during the sol-gel process rather than by grafting. Samples were thoroughly characterized by TEM, X-ray diffraction, FT-IR, DR-UV/Vis and their texture has been examined by nitrogen adsorption–desorption at 77 K. The photocatalytic activity for the degradation of p-nitrophenol and Escherichia coli and Lactobacillus rhamnosus bacteria cells in aqueous medium, under halogen lamp light have been evaluated in relation with the physico-chemical modifications induced by the doping.
The low temperature vacuum drying protocol (150°C) used in the present study enabled to obtain porphyrin doped TiO2 xerogels with a high specific surface area, and containing nanoparticles composed of amorphous- and anatase-TiO2. Diffuse reflectance spectroscopy attest the presence of TCPPH2 and TCPPNi within the TiO2 matrix. In a first step, the photoactivity of the xerogels is tested for p-nitrophenol degradation. Results show that crystallinity and nature and concentration of porphyrin introduced in situ have major impact on the degradation performances. In a second step, the best xerogel for p-nitrophenol degradation has been used to degrade bacteria. This xerogel degrades E. coli and L. rhamnosus bacteria cells in less than 48 and 24 h respectively. The photocatalytic degradation of a pollutant is thus correlated to the degradation of bacteria since a xerogel doped with the TCPPNi degrades both p-nitrophenol, E. coli and L. rhamnosus.