Applying both kinetic and thermodynamic measures to promote solar-driven photocatalytic ozonation on defect-engineered porous tungsten oxide

Mass transfer of ozone within the inner structure of a catalyst and utilization efficiency of the photo-generated electrons are two decisive factors governing the production of hydroxyl radicals ( • OH) in photocatalytic ozonation process from kinetic and thermodynamic perspectives, respectively. For achieving precise dual-control, defect-engineered tungsten oxide with a periodic porous architecture (p-WO 3-OV ) is synthesized. Compared with pristine WO 3 , p-WO 3-OV achieves a 7.6-fold increase in the reaction rate of solar photocatalytic ozonation, accompanied by a 2.3-fold enhancement in the ozone utilization efficiency . The constructed periodic porous structure shortens the migration path of charge carriers and promotes the fluidity of the reactants. The rich oxygen vacancies in WO 3 enhance the generation of charge carriers and promote O 3 interactions. This work provides mechanistic insights into both the kinetic boost endowed by porous nanoarchitecture, and the thermodynamic modulation enabled by defect engineering to achieve the synergy in solar-driven photocatalytic ozonation. • Defect-engineered tungsten oxide with a periodic porous structure was synthesized. • Oxygen vacancies improved separation of charge carriers and enhanced O 3 adsorption. • Periodic porous structures boosted the internal mass transfer within the catalysts. • High ozone and electron utilization efficiencies were achieved. • The optimized kinetics and thermodynamics enhanced • OH generation.