Time-resolved spectroscopic investigation for the practical application of a photocatalytic air purifier

The photocatalytic efficiency for removing volatile organic compounds (VOCs) is significantly influenced by operational parameters like humidity and flow velocity, exhibiting notable and inconsistent fluctuations in both lab-scale and large-scale demonstrations. In this study, operando spectroscopy and isotope analysis were employed to investigate the correlation between humidity levels and degradation of gaseous acetaldehyde using TiO₂ photocatalysts, aiming to demonstrate the scaling-up of photocatalytic air purifier. It was observed that rate constants for the mineralization of acetaldehyde rapidly decreased by 30% as relative humidity increased from 25% to 80% in the flow system (with an air velocity, v = 0.78 m/s). However, batch system showed smaller change with only a 10% reduction of the rate constant. Humidity fluctuations were more pronounced under high-speed conditions and were amplified in air purifier (v = 3.8 m/s). Time-resolved operando spectroscopy using an ¹³C isotope of acetaldehyde revealed that humidity's distinct role in dark adsorption and photocatalytic reactions. Water was found to inhibit the formation of crotonaldehyde during aldol condensation reaction in dark condition. Moreover, water suppressed photocatalytic mineralization by inhibiting acetate oxidation to formate. These findings provide valuable insights for improving realistic air purification processes, underscoring the importance of identifying key intermediates and controlling humidity to enhance the selectivity of gaseous pollutant oxidation reactions.