Constructing dual-functional porphyrin-based thorium metal-organic framework toward photocatalytic uranium(VI) reduction integrated with organic oxidation

The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(VI) reduction and value-added organic oxidation, is highly desirable but remains huge challenge. Here, we couple the photocatalytic U(VI) reduction with the oxidative organic synthesis to one system using novel extended π-conjugated framework (Cu@Th-TCPP) without the expense of sacrificial reagents. Noticeably, the as-prepared Cu@Th-TCPP linked by tetratopic tetrakis(4-carboxyphenyl)porphyrin (TCPP) ligand and unique Th6(μ3-O)2(HCOO)4(H2O)6 secondary building unit (SBU) exhibits significantly enhanced activity when the photocatalytic U(VI) reduction and thioanisole oxidation were integrated to one system. Further experimental characterizations demonstrate that the highly conjugated framework of Cu@Th-TCPP is good for the charge transfer and separation, while incorporating Cu2+ site further accelerates the charge-carrier dynamics, thus giving rise to the dual-functional property. Apparently, this strategy conforms to atomic economy, opens a new horizon to addresses radioactive environmental pollution in natural water systems and soils, and simultaneously produces valuable chemicals.