Online Detection of Reactive Oxygen Species in Ultraviolet (UV)-Irradiated Nano-TiO₂ Suspensions by Continuous Flow Chemiluminescence

Reactive oxygen species (ROS) play very important roles in the photocatalytic reactions of semiconductors. Using a continuous flow chemiluminescence (CFCL) system, we developed three methods for the selective, sensitive, and online detection of O2(• -), •OH, and H2O2 generated during ultraviolet (UV) irradiation of nano-TiO2 suspensions. TiO2 nanoparticles were irradiated in a photoreactor and pumped continuously into a detection cell. To detect O2(• -), luminol was mixed with TiO2 before it entered the detection cell. For the detection of short-lived •OH, phthalhydrazide was added into the photoreactor to capture •OH, and then mixed with H2O2/K5Cu(HIO6)2 to produce chemiluminescence (CL). To detect H2O2, an irradiated TiO2 suspension was kept in darkness for 30 min, and then mixed with luminol/K3Fe(CN)6 to produce CL. The selectivity of each method for a particular ROS was verified by using specific ROS scavengers. For a given ROS, a comparison between CL and conventional method showed good agreement for a series of TiO2 concentrations. The sensitivity of CL method was approximately 3-, 1200-, and 5-fold higher than the conventional method for O2(• -), •OH, and H2O2, respectively. To demonstrate the utility of the methods, ROS in three different types of TiO2 suspensions was detected by CFCL. It was found that photodegradation efficiency of Rhodamine B correlated the best (R(2) > 0.95) with the amount of photogenerated •OH, implying that •OH was the major oxidant in Rhodamine B photodegradation reaction. CFCL may provide a convenient tool for the studies on the reaction kinetics of ROS-participated decomposition of environmental contaminants.