Metalloporphyrin modified defective TiO2 porous cages with the enhanced photocatalytic activity for coupling of hydrogen generation and tetracycline removal

Integration of molecular transition-metal complexes and semiconductors is an appealing method to develop high-performance hybrid photocatalysts based on improvement of their solar energy harvesting ability and photogenerated charge carrier separation efficiency. Herein, Cu-TCPP modified TiO2 porous cages with oxygen vacancy defects, derived from NH2-MIL-125(Ti) nanocrystals, are successfully prepared to form PC-TiO2-d/Cu-TCPP hybrids via a surface assembly process. The PC-TiO2-d/Cu-TCPP hybrid shows an enhanced photodegradation efficiency (73.7%, 95.4%) towards tetracycline in the air under visible light or the simulated sunlight irradiation compared to PC-TiO2-d (33.7%, 81.1%) within 100 min. Moreover, the photocatalytic system is applicable to coupling both processes of solar fuel production and pollutant degradation. The PC-TiO2-d/Cu-TCPP hybrid exhibits a high hydrogen evolution rate of ∼2 mmol g-1 h-1 in the aqueous solution of tetracycline in an inert atmosphere upon irradiation by the simulated sunlight. In contrast, an inferior photocatalytic performance of hydrogen evolution is observed in pure water without the addition of tetracycline. Finally, the high sustainability of PC-TiO2-d/Cu-TCPP is mainly attributed to the strong interaction between the molecular photosensitizer and the semiconductor photocatalyst by oxygen vacancies and Cu(ii) ions.