Efficient structure tuning over the defective modulated zirconium metal organic framework with active coordinate surface for photocatalyst CO₂ reduction

Structure engineering of zirconium-based metal organic frameworks (MOFs) aims to develop efficient catalysts for transforming intermittent renewable energy into value-added chemical fuels. In order to have a deeper understanding of industrial scaling, it is vital to ascertain the favourable operational parameters that are necessary for projecting at the atomic level. The proposed paradigm provides a robust basis for the efficient design of MOFs based heterogeneous photocatalysts. In this study, set of defective MOF (D-NUiO66) was effectively produced using a modular acidic method. Afterwards, the D-NUiO66 was combined with CeO₂ to form the D-CeNUiO66 heterojunction for the purpose of carbon dioxide reduction. The morphological aspect of the composite investigation suggested that D-CeNUiO66 had a mesoporous structure with favourable adsorption properties. The optimized D-CeNUiO66 photocatalyst showed the high activity for the reduction of CO₂ to CO, with a rate of 38.6 µmolg⁻¹h⁻¹ and demonstrated remarkable repeatability in terms of CO production. The incorporation of defect sites in the D-NUiO66 enhanced the light response to visible light, resulting in reduced band gap of 2.9 eV. The photoelectrochemical tests indicated that the introduction of defects in the UiO66 and coupling CeO₂ in the D-CeNUiO66 composite induced fast charge transfer, therefore suppressing the charge recombination rate. This study provides valuable insights into the use of defective engineering and heterojunction approaches to metal–organic frameworks for photocatalytic applications.