Photocatalytic oxidation of MEK over hierarchical TiO2 catalysts: Effect of photocatalyst features and operating conditions

A novel hydrothermal route was developed to synthesize crystalline and hierarchically porous TiO2 at mild conditions under acidic/basic reaction environments. A good control over the key features of catalysts could be achieved by varying the pH of the starting solution (pH = 2-12) and type of acid during preparation. Crystalline, textural, and optical properties of photocatalysts were characterized in order to explore the connections between catalysts' features and photoactivity. The activities of catalysts were evaluated for decomposition of methyl ethyl ketone (MEK) in a continuous flow photoreactor. To gain insight into the impact of main operating conditions on photocatalytic oxidation (PCO) processes, experiments were conducted at wide ranges of inlet concentration, relative humidity, and residence time. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that yielded titania samples possess good crystallinity and mainly consist of anatase polymorph. Results of X-ray photoelectron spectroscopy (XPS) indicated that the population of hydroxyl groups on the surface of TiO2 declines as the acidity of hydrothermal solution increases. Hierarchical porous structure with ultra-long parallel macrochannels and large macropores (> 0.5 mu m) could be directly observed in scanning electron microscopy (SEM). The multimodal porous structure offers higher light utilization, enhanced mass transport, and superior adsorption capacity for air pollutants. Photoluminescence spectroscopy revealed that the enhancement in crystallinity has an impact on the separation of photo-induced charge carriers. Moreover, a satisfactory linear correlation between the ability of photocatalysts to generate *OH and crystallinity could be found. Under the harshest operating condition (residence time = 0.012 s, relative humidity = 50%, concentration = 1000 ppb), the TiO2 synthesized in nitric acid (pH = 4) achieved the highest MEK removal efficiency, 36.9%, which substantially surpassed that of P25, 14.5%. Hierarchical porosity, optimum trade-off between surface area and crystallinity, existence of meso- and macropores, small crystal size, and high (OH)-O-center dot generation ability could account for the superior performance. A tentative reaction pathway for MEK photo-degradation and a health-risk index were put forward considering the by-products detected in the gas phase.