Activation Treatments and SiO2/Pd Modification of Sol–Gel TiO2 Photocatalysts for Enhanced Photoactivity under UV Radiation

Julien Mahy,Sophie Hermans,Stéphanie Lambert,Ludivine Tasseroul,Valériane Sotrez

doi:10.3390/catal10101184

Abstract

The objective of this work is to improve the efficiency of TiO2 photocatalysts by activation treatments and by modification with palladium nanoparticles and doping with SiO2. The influence of the additive loading was explored, and two activation treatments were performed: UV exposition and H2 reduction. TiO2/SiO2/Pd photocatalysts were synthesized by an original cogelation method: a modified silicon alkoxide, i.e., [3-(2-aminoethyl)aminopropyl]trimethoxysilane (EDAS), was used to complex the palladium ions, thanks to the ethylenediamine group, while the alkoxide groups reacted with TiO2 precursors. Pure TiO2 was also synthesized by the sol–gel process for comparison. X-ray diffraction evidenced that the crystallographic structure of TiO2 was anatase and that Pd was present, either in its oxidized form after calcination, or in its reduced form after reduction. The specific surface area of the samples varied from 5 to 145 m2 g-1. Transmission electron microscopy allowed us to observe the homogeneous dispersion and nanometric size of Pd particles in the reduced samples. The width of the band gap for pure TiO2 sample, measured by UV/Visible diffuse reflectance spectroscopy at approximately 3.2 eV, corresponded to that of anatase. The band gap for the TiO2/SiO2/Pd composite samples could not be calculated, due to their high absorption in visible range. The photocatalytic activity of the various catalysts was evaluated by the degradation of a methylene blue solution under UV radiation. The results showed that the photocatalytic activity of the catalysts was inversely proportional to the content of silica present in the matrix. A small amount of silica improved the photocatalytic activity, as compared to the pure TiO2 sample. By contrast, a high amount of silica delayed the crystallization of TiO2 in its anatase form. The activation treatment under UV had little influence on photocatalytic efficiency. The introduction of Pd species increased the photocatalytic activity of the samples because it allowed for a decrease in the rate of electron–hole recombinations in TiO2. The reduction treatment improved the activity of photocatalysts, whatever the palladium content, thanks to the reduction of Ti4+ into Ti3+, and the formation of defects in the crystallographic structure of anatase.

Highlights

Different processes have been developed to reduce the current pollution in water, air and soil [1,2]
Six samples were prepared: one pure titania, one titania doped with silica and four titania samples doped with silica and modified with Pd named
TiO2 /SiO2 /PdX, where X corresponds to the theoretical wt.% of Pd and can vary between 1, 5, and 22 wt.% of Pd

Summary

Introduction

Different processes have been developed to reduce the current pollution in water, air and soil [1,2]. Its activation produces a series of redox reactions leading to radicals’ formation. These radicals can attack organic pollutants and degrade them in CO2 and H2 O if the degradation is complete [3,4]. The most used photocatalyst is TiO2 [5,6,7] This material is activated under UV light due to its band gap around 3.2 eV for the anatase phase [4]. The use of TiO2 as photocatalyst has two main limitations [4]:

Objectives

Methods

Results