Zr-MOF Nanosheets Featuring Benzothiadiazoles Enable Efficient Visible Light Driven Photooxidation of Sulfides and Amines

Ultrathin zirconium-based metal−organic framework (MOF) nanosheets, embedded with photochromic units, are expected to be highly efficient heterogeneous photocatalysts, thanks to their rich catalytic sites, short diffusion paths, and effective separation of photogenerated charge carriers. Herein, we reported the synthesis of novel Zr-MOF nanosheets (Zr-BTDB) through a solvothermal synthesis that integrates benzothiadiazole (BTz) as a photochromic moiety within the framework of MOF. The Zr-BTDB nanosheets processes a [Zr₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆] cluster with hcp topology. Importantly, Zr-BTDB nanosheets exhibit excellent photocatalytic activity for the photooxidation of sulfides and amines at room temperature under blue light irradiation. Notably, these nanosheets maintain their photocatalytic activity and selectivity for up to five cycles without significant loss of activity and crystallinity. Systematical catalytic reactions revealed that the Zr-BTDB nanosheets enable the generation of singlet oxygen (¹O₂) and superoxide radical (O₂⋅⁻) under visible light irradiation, which is critical reactive oxygen species for the photooxidation of sulfides and benzylamines. Our work represents a straightforward route for the preparation of ultrathin, water stable, and visible-light-activated Zr-MOF nanosheets, offering new potentials for the selective photooxidation of sulfides and amines in an eco-friendly way.