Synthesis of cerium-doped MCM-41 for ozonation of p-chlorobenzoic acid in aqueous solution

Abstract

Cerium-doped MCM-41 (Ce-MCM-41) was prepared by a hydrothermal method and its catalytic activity for ozonation of p-chlorobenzoic acid (p-CBA) in aqueous solution was studied. For comparison, cerium-loaded MCM-41 (Ce/MCM-41) was prepared by a dipping method. Ce-MCM-41 was characterized by the low and wide angle X-ray powder diffraction (XRD), nitrogen adsorption–desorption, transmission electron microscopy (TEM) and ultraviolet–visible diffuse reflection spectrum (UV–vis DRS). The results showed that the material retained the highly ordered mesopore structure of MCM-41 and had a surface area of 852m2g−1. Cerium was incorporated into the framework of MCM-41, locating at tetrahedrally coordinated sites. The cerium doping content, initial pH of aqueous solution and reaction temperature played important roles in catalytic ozonation of p-CBA. Under the chosen conditions (1.39mgl−1 ozone dosage, 10mgl−1p-CBA solution and 1gl−1 catalyst dosage), the high mineralization rate (86%) was achieved by Ce-MCM-41/O3 process at 60min reaction time, only 52% by O3 alone. The combination of Ce-MCM-41 and O3 exhibited a significant synergetic effect. Ce-MCM-41 showed the better activity and stability than cerium-loaded MCM-41(Ce/MCM-41) during catalytic ozonation of p-CBA, its cerium leaching was greatly reduced (only 0.085mgl−1) and below detection limit after being reused, compared with that of Ce/MCM-41 (0.44mgl−1) with the presence of the same theoretical cerium content. TOC removal rate slightly decreased from 86% to 81% and kept stable after Ce-MCM-41 being re-utilized two times, which illustrated that Ce-MCM-41 was a kind of promising catalyst for ozonation of p-CBA. The addition of Ce-MCM-41 significantly improved ozone decomposition into HO in aqueous solution and reduced ozone concentration in equilibrium.