Pathway analysis of phenol degradation by UV/TiO2 photocatalysis using the Carbon-13 isotopic labelling technique

Abstract

The United States Environmental Protection Agency (USEPA) has enlisted phenolic compounds as pollutants of priority concern, as they tend to persist in the environment over a long period, accumulate and exert toxic effects on humans and animals. The entrance of phenolic compounds into the aquatic environment results from natural, industrial, domestic and agricultural activities. Their presence may be due to the degradation or decomposition of natural organic matter present in the water, through the disposal of industrial and domestic wastes into water bodies and through runoffs from agricultural land. Several specific new technologies, called Advanced Oxidation Processes (AOP), have been developed to eliminate dangerous organic chemicals such as phenol from polluted waters. The photocatalytic process, based on UV irradiated semiconductor (TiO2), represents one of AOP that provide an interesting route to the destruction of many organic substances to CO2 , H2O and corresponding mineral acids. TiO2 is usually used as a photocatalyst in two crystal structures: Rutile and Anatase. The photoreactivity of P-25 Degussa, consisting of anatase and rutile (4/1 w/w), exceeds that of pure anatase and rutile in several reaction systems. This study characterised the three TiO2 powder forms by BET, XRD, XRF and SEM analyses to contribute to a better understanding of their physical properties. Anatase was revealed to have 98.4% purity x-ray fluorescence analysis, Degussa at 96.7% and rutile at 75.7% was reported to have the most impurities (~25%). This study investigated the UV/TiO2 photocatalytic degradation of phenol, with emphasis on the effects of; solution pH, catalyst load, initial phenol concentration, dissolved oxygen and UV radiation intensity. Degradation studies were conducted in a batch reactor with photons for catalyst (TiO2) activation supplied by a medium pressure 400 W UV lamp immersed in the pollutant solution housed in a double jacket quartz sleeve, which served as the cooling system for the lamp. Temperature control in the reactor was achieved by circulating cold water through the outer cavity of the quartz sleeve. The reactor contents in all batches were aerated at a flow rate of 10 mL/min. Thorough mixing of the contents of the reactor was achieved by continuous agitation with a magnetic stirrer. The experimental reaction time was set at 60-100minutes. Samples were monitored by GC-MS analysis. Results showed that UV/TiO2 photocatalysis is an effective method for the removal of phenol from wastewaters. The efficiency of the process depends strongly on the experimental conditions. Degradation of organic compounds in water is often accompanied by the formation of several intermediate compounds, some of which may be more toxic than the original pollutant. The carbon-13 isotopic labelling technique was employed to track the degradation mechanism of phenol to better understand the degradation pathway. Carbon-13 tracking results revealed that hydroquinone, catechol, benzoquinone, resorcinol and maleic acid were the main intermediates containing the C-13 isotope. A reaction pathway was postulated based on these findings. Kinetic isotope effect (KIE) experiments were conducted and a primary isotope effect was observed. This confirmed that the C-13 isotope position on the labelled phenol was the site of bond breaking in the rate-limiting step.